JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 114, B07202, doi:10.

1029/2008JB005928, 2009

Experimental investigations of the wettability of clays and shales

Artem Borysenko,1 Ben Clennell,2 Rossen Sedev,1 Iko Burgar,3 John Ralston,1
Mark Raven,4 David Dewhurst,2 and Keyu Liu2
Received 14 July 2008; revised 26 February 2009; accepted 14 April 2009; published 11 July 2009.

[1] Wettability in argillaceous materials is poorly understood, yet it is critical to

hydrocarbon recovery in clay-rich reservoirs and capillary seal capacity in both caprocks
and fault gouges. The hydrophobic or hydrophilic nature of clay-bearing soils and
sediments also controls to a large degree the movement of spilled nonaqueous phase
liquids in the subsurface and the options available for remediation of these pollutants. In
this paper the wettability of hydrocarbons contacting shales in their natural state and the
tendencies for wettability alteration were examined. Water-wet, oil-wet, and mixed-wet
shales from wells in Australia were investigated and were compared with simplified
model shales (single and mixed minerals) artificially treated in crude oil. The intact natural
shale samples (preserved with their original water content) were characterized
petrophysically by dielectric spectroscopy and nuclear magnetic resonance, plus scanning
electron, optical and fluorescence microscopy. Wettability alteration was studied using
spontaneous imbibition, pigment extraction, and the sessile drop method for contact angle
measurement. The mineralogy and chemical compositions of the shales were determined
by standard methods. By studying pure minerals and natural shales in parallel, a
correlation between the petrophysical properties, and wetting behavior was observed.
These correlations may potentially be used to assess wettability in downhole
measurements.
Citation: Borysenko, A., B. Clennell, R. Sedev, I. Burgar, J. Ralston, M. Raven, D. Dewhurst, and K. Liu (2009), Experimental
investigations of the wettability of clays and shales, J. Geophys. Res., 114, B07202, doi:10.1029/2008JB005928.

1. Introduction constituting the seal are naturally hydrophobic, or become

[2] Trapping and retention of nonaqueous phase liquids
are important considerations for the petroleum industry and
also for the prevention and remediation of environmental
damage associated with the spillage of chemical products or
waste. A successful study of liquid distribution and liquid/
liquid displacement in complex mineral systems (e.g.,
porous sediments or soils) requires the development of
reliable techniques for wettability and surface characteriza-
tion. The majority of research on the dynamics and trapping
of nonaqueous fluids has focused on granular geomaterials
such as sandy aquifers and sandstone reservoirs, while the
fine-grained and clay-rich lithologies that typically retard or
trap nonaqueous phase liquids have received much less
attention. A mud or a shale layer in the subsurface is usually
assumed to act as a perfect seal to the nonaqueous phase.
The implicit assumption is that fine, clay-rich rocks are
inherently water-wet (i.e., hydrophilic) so that a capillary
pressure barrier is formed. If the surfaces of minerals
1
Ian Wark Research Institute, University of South Australia, Mawson
Lakes, South Australia, Australia.
2
CSIRO Petroleum, Kensington, West Australia, Australia.
3
CSIRO Materials Science and Engineering, Clayton South, Victoria,
Australia.
4
CSIRO Land and Water, Urrbrae, South Australia, Australia.
Copyright 2009 by the American Geophysical Union.
0148-0227/09/2008JB005928$09.00
so with time, then the supposed barrier may leak, and
retardation of oil or contaminant flow through the seal will
happen only by virtue of its low effective permeability.
2. Specific Aims and Scope of the Present Study
[3] Shales/mudrocks act as seals to petroleum reservoirs
because of their low permeability and high capillary entry
pressure. Capillary sealing requires that the rock is substan-
tially water-wet. Typically, a zero contact angle for water is
assumed for shales, though this is not usually confirmed by
measurements [Anderson, 1986a]. There is mounting evi-
dence that shales become (patchily) oil-wet through in situ
maturation of organic matter [Boult et al., 1997] or exposure
to polar compounds in formation waters [Larter and Aplin,
2005]. It is therefore worthwhile testing the wettability of
shale caprocks through controlled experiments. The ulti-
mate aim of this research is to compile a database combin-
ing geological information about caprocks and relationships
of these parameters to their physico-chemical properties,
which are assessed by X-ray diffraction (XRD), scanning
electron microscope (SEM) and cation exchange capacity
(CEC) as well as bulk chemistry and wettability tests. A
secondary aim is to investigate which petrophysical
methods may be used to predict these properties from
downhole log data or rapid nondestructive tests on core
samples. While the focus here is on mudrocks, the

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Table 1. Samples Used in This Study

Sample Code Sample Composition and Treatment
Q Quartz clean (hydrophilic): cleaned with sulphuric acid and potassium hydroxide
QM Quartz methylated (hydrophobic): cleaned as above and then methylated with TMCS
M Montmorillonite clay
M+Q Montmorillonite clay (10%) added into coarse quartz (90%)
K Kaolinite
L1_390 Hydrophilic shale (quartz 20%, orthoclase 11%, illite 49%, chlorite 2%, hematite 5%, dolomite 13%) CEC = 30 cmol/kg;
SSA = 9.2 m2/g
O1A Hydrophobic shale (quartz 41%, kaolin 42%, mica 16%, hematite < 1%, siderite < 1%) CEC = 13 cmol/kg; SSA = 3.3 m2/g
xxx-C Sample xxx, treated in crude oil (70C for 24 h)
xxx-CW Sample xxx, treated in crude oil and exposed to water (rehydrated)

methods developed will be useful in formation evaluation
of shaly sands, to give an indication of wettability at an
early stage and/or to monitor wettability changes that may
occur in the critical near-wellbore region during produc-
tion from clay-rich reservoirs.
[4] To understand wettability, we need to study several
parameters of the system, such as surface texture, micro-
morphology of the porosity, brine composition and oil
composition and phase state at the prevailing pressure-
volume-temperature conditions [Drummond and Israelachvili,
2004]. In this study, it is necessary to consider shales as
multimineral composites with wetting behavior influenced
by their various components. Other parameters that affect
wettability are the chemical composition and physicochem-
ical properties of the brine and the crude oils, which vary
depending on the nature of the source rocks, maturation
history, migration, biodegregation and so on [Buckley,
2001]. Effective, nondestructive methods are required to
monitor the various aspects of fluid-rock interaction. High-
resolution methods such as environmental scanning electron
microscopy (ESEM) and atomic force microscopy (AFM)
are valuable tools to directly probe mineral surfaces and
identify adsorbed species, but less useful when one attempts
to understand processes occurring throughout a porous
medium under dynamic conditions of fluid displacement.
Thus optical and fluorescence microscopy, scanning electron
imaging as well as NMR spectroscopy and dielectric meas-
urements are used to assess liquid/solid interactions and
liquid mobility within the pores space of a model rock
composed of packed powdered shale, clay or quartz samples.
These methods have a substantial history in rock wettability
research [Anderson, 1986b; Buckley, 2001; Morrow and
Mason, 2001] but they have rarely been used in combina-
tion, and few studies have been conducted specifically on
clays and shales.
3. Materials and Methods
[5] The same physico-chemical interactions that control
interfacial interactions in the subsurface also exert a com-
bined effect on wettability measurements made in the
laboratory. As a result, we had to divide this study into
several steps and build up knowledge of the individual
phenomena involved [Clennell et al., 2006]. Each method
probes one or more fundamental properties or processes
(e.g., hydrophobicity, adhesion forces, displacement kinet-
ics, swelling, etc.). By applying several methods together
and complementing them with direct microscopic observa-
tions and spectroscopic analysis, we obtain an understand-
ing of how these competing effects interact in natural
scenarios.
3.1. Samples
[6] Initially, simple model systems (Table 1) were used:
quartz silt (Q), montmorillonite clay (M) and its mixture
with quartz (M+Q), kaolinite (K). The quartz surfaces were
thoroughly cleaned using sulphuric acid, hydrogen peroxide
and potassium hydroxide to ensure a high level of surface
cleanliness. Under such conditions, the quartz surface is
strongly hydrophilic. Surface modified quartz (QM) was
produced by reacting clean and dry samples with trimethyl-
chlorosilane (TMCS). TMCS reacts with the hydroxyl
groups (silanols) present on the surface of quartz. Tri-
methyl groups are thus chemically grafted onto the surface
which then becomes hydrophobic. To explore the effects of
natural wettability variation two shales from Australia were
chosen: (1) a sample from the Bass Basin (O1A), which
contains quartz and kaolin and is hydrophobic, and (2) a
sample from the continental Officer Basin in Western
Australia (L1_390), which contains abundant illite and is
strongly hydrophilic (Table 1). The shales were examined in
an original state of preserved water content (taken from
the drill core and stored under oil) and also in a dried and
powdered form. It was verified that the interior parts of the
preserved shales were not penetrated by the storage oil
(Shell P-874, containing alkanes and napthenes), using
fluoresence microscopy on the broken open surface: no
fluorescence was detected [Liu and Eadington, 2005].
[7] For microscopic observations and the sessile drop
method, flat fragments of rocks were used. For imbibition
and pigment extraction as well as in dielectric and NMR
measurements, granulated shale samples (150 180 mm
grain size) were examined, focusing our attention on wet-
tability effects as well as accessing a large internal surface
of the multimineralic shales without requiring extraordinarily
high capillary pressures [Diggins and Ralston, 1993]. In the
imbibition tests we were using highly refined oil (Shell
Ondina 15, that is nonadditive, aromatic free, paraffinic
white mineral oil). In order to study the wettability changes
after interaction with crude oil, we tested the quartz silt, clay
and granulated shales before and after a simplified aging
process (heating in oil at 70C for 24 h). Dupuy Crude, from
Western Australia was used for the treatment (44 45 API,
h20C = 1.59 mPa s).
3.2. Contact Angle Measurement
[8] The contact angle, the basic characteristic of wetta-
bility, can be easily observed and measured considering a

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B07202 BORYSENKO ET AL.: WETTABILITY OF CLAYS AND SHALES
Figure 1. Sessile drop tests. (a) A water droplet on the air
dry surface of hydrophilic shale L1_390 in original state.
(b) Example of a water droplet on the air dry surface of an
oil-wet reservoir rock from the Perth Basin, Western
Australia. (c) Measurement of oil/water contact angle made
with a water droplet under hexadecane on the surface of
crude oil treated shale sample L1_390-C. (d) Water droplet
under the same oil-immersed conditions for a treated shale
sample O1A-C.
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B07202
drop of liquid sitting on a flat fragment of a mineral as in
Figure 1 [Anderson, 1986b]. The contact angle on a
hydrophilic surface is low (Figure 1a). On the hydrophobic
surface of a naturally oil-wet reservoir rock (a shaly
sandstone from a field in the Perth Basin) water formed a
drop with a sharp mineral/water/air contact line, displaying
a contact angle of 110 (Figure 1b). The advancing contact
angle was determined by recording and analyzing digital
images of a drop of liquid on the mineral surface [Kumar et
al., 2005; Shedid and Ghannam, 2004; A. Borysenko et al.,
Wettability measurements in model and reservoir shale
systems, SCA International Symposium, Trondheim, Soci-
ety of Core Analysts, Norway, 12 16 September 2006].
The accuracy of the measurement is affected by the rough-
ness and heterogeneity of the surface [Neumann and Good,
1979] despite the fact that flat quite smooth fragments were
purposely selected. The different contact angles on the left
Figure 2. Cell for forced imbibition tests. It consists of a
glass tube 20 cm long (30 mm inner diameter), Teflon caps
(consisting of plug which is inserted directly in the tube and
screws to fix inlet and outlet tubes), rubber O-rings to make
the cell waterproof, and inlet and outlet pipes (3 mm inner
diameter).
B07202 BORYSENKO ET AL.: WETTABILITY OF CLAYS AND SHALES B07202

Figure 3. Decrease of air-water contact angle on hydrophobic shale O1A (solid triangles); kaolinite
(solid squares), montmorillonite (open squares); hydrophilic shale L1_390 (open triangles). Vertical bars
indicate the error due to surface roughness and heterogeneity (estimated from 10 individual
measurements made across the sample).

and right side of the droplet in Figure 1b illustrate this
clearly. The contact angles reported here are an average over
at least 10 measurements on different locations of the solid
sample. The precision of our contact angle measurements is
5 or better.
3.3. Liquid-Liquid Extraction
[9] A disadvantage of the sessile drop method is that it
requires a relatively large flat area. For small particles a
more suitable technique is film (or skin) flotation technique
[e.g., Fuerstenau et al., 1991]. During the test, 1 g of
granulated sample (grain size <10 mm) was placed inside
the separating funnel together with 20 mL of water and
20 mL of a single component oil (hexadecane). The funnel
was thoroughly shaken for 5 min and allowed to settle. As a
result of the competition between oil and water for the
surfaces, some particles sank in the water while other
particles kept floating in the oil depending on their wetta-
bility. The distribution of particles between the oil and water
phases provides a quantitative measure of the hydrophobic-
ity of the shale.
3.4. Spontaneous and Forced Imbibition
[10] A more realistic assessment of wettability in the
porous medium of a shale is obtained through imbibition
experiments. The effect of interfacial interactions can be
characterized by the rate and quantity of oil recovery during
spontaneous imbibition [Morrow and Mason, 2001]. In the
spontaneous imbibition test, the mineral powder is packed
into a small vial, then fully saturated with crude oil and,
after that, immersed in a sealed glass container full of water.
The oil recovery, relative to the original oil in place (% ohmic conductivity. Samples with higher water content
OOIP), was monitored by measuring the volume of oil
expelled from the sample. Thus we follow how the fluid
initially present is displaced by a second immiscible fluid
with a higher affinity for the solid surface.
[11] In forced imbibition tests, the displacing liquid is
driven by an externally applied pressure. In this case, the
measurement of permeability was obstructed by intensive
water adsorption by clays so of particular interest were the
capillary entry pressure (for the nonwetting phase to pene-
trate the packed bed), the relative permeability to water and
oil, the sweep efficiency (residual saturation) and the spatial
distribution of the trapped fluid on the pore scale.
[12] The apparatus used for the forced imbibition test is
presented in Figure 2. Packed beds of shale particles (100
250 mm size) were used because it is impractical to force
fluids through intact shales. The packed beds present a large
mineral area to the invading and retained fluid and therefore
adequately reflect the wettability of the mineral assemblage.
The pressure generated by a water injection (at constant
flow rate) was monitored with time.
3.5. Dielectric Methods
[13] The dielectric constant of a porous material is
strongly affected by fluid content and distribution. Water
has a high dielectric constant (
80) compared with mineral
grains or oils (typically 4 5). At high frequency (1 3 GHz),
the value of the dielectric constant reflects mainly the
amount of water compared with air, solids and oil (accord-
ing to a volumetric mixing law) [Sweeney et al., 2007].
Surface active clay-rich materials and samples with multiple
fluid films exhibit a greater dielectric constant at low
frequencies 1 100 MHz. The value of the dielectric con-
stant at around 10 MHz depends on fluid proportions,
thickness of the adsorbed films and mineralogy. Changes
in dielectric constant over time can be used as a sensitive
measure of liquid redistribution in the sample. The dielectric
loss at low frequency (<100 MHz) depends mainly on
and more clay show a greater loss i.e., are less resistive
than samples with low water content or without clay.
[14] After initial frequency sweep tests to determine a
suitable frequency that shows substantial changes with fluid
saturation, a single frequency of 10 MHz for presentation of
dielectric results was chosen. Our dielectric measuring
system consisted of a Vector Network Analyzer (Agilent

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Figure 4. Results of liquid-liquid extraction tests. Distributions of particles (size 1 mm) between water
and oil (South Australian light crude, 45 API). Powdered shales (O1A and L1_390) and minerals (Q,
quartz; M, montmorillonite; K, kaolinite) were tested (a) before and (b) after aging in crude oil (70 for
24 h).

ENA 5071B) and a coaxial probe (end-loaded transmission
line) 6 mm in diameter that was placed against the sample.
The software (Agilent 5071A) returns both the real part of
the relative permittivity (dielectric constant) and the imag-
inary relative permittivity (dielectric loss) at each frequency.
The dielectric spectra therefore consist of two continuous
functions that are relatively smooth in variation with fre-
quency over the interval of measurement. A more familiar
parameter, resistivity, r, was calculated from the dielectric
loss, e00, as r = (2p f e0e00)1, where f is frequency and e0 is
the permittivity of free space.
[15] Measurements were started with powdered shale
pretreated in crude oil and then water was added drop-wise
up to around 80% saturation. After each hydration step, the
weight change was measured and a dielectric spectrum was
acquired. At each point, sufficient time (from several
minutes to several hours) was allowed for stable values of
the real and imaginary permittivity to be obtained.
3.6. NMR Methods
[16] The displacement processes in either spontaneous or
forced imbibition may be monitored by proton NMR
spectroscopy [Chen et al., 2006; Fleury and Deflandre,
2003; Manalo et al., 2003]. The most straightforward
analysis method is determination of the bulk sample trans-
verse nuclear spin relaxation time decay. T2 was obtained
with a low field NMR spectrometer (2 MHz Maran Ultra)
using the Carr-Purcell-Meiboom-Gill (CPMG) pulse se-
quence in a uniform magnetic field. The low-field NMR
methods probe a sample volume of 20 70 cm3 and require
about 1 5 g of hydrogen-bearing liquid in the sample to
produce reliable results. The advantage is relative insensi-
tivity to the magnetic susceptibility contrasts of grains and
matrix that are problematic in real rocks if measured at high
magnetic fields.
[17] A conventional regularized least squares inversion
routine was used to invert the decaying echo train to a T2
spectrum. In the Maran Ultra instrument, the initial echo
signal is detected after an interval of around 250 ms and with
230 ms interecho spacing, so only liquid-borne protons with
a spin lifetime of at least tens of ms are detected. Practically
this means that liquids in pores of all sizes down to
hundreds of nanometer are completely detected, together
with some fluid in smaller pores and bound to surfaces.
Surface- and solid-bound protons and protons in nanometer-
sized pores are not detected with this instrument. The T2
value for bulk water is around 3 s, while that for Ondina 15
oil is 115 ms. The South Australian light crude oil has a
multiexponential T2 distribution centered around 100 ms.
4. Results and Discussion
4.1. Wettability
[18] The L1_390 shale is water wet in its natural (un-
treated) state as are many shales. In this case water spon-
taneously spreads on their surface (Figure 1a) and the

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Figure 5. Curves illustrating the progress of spontaneous imbibition by showing the percentage of oil
displaced by water versus time: clean quartz (open circles), hydrophilic shale L1_390 (open triangles),
kaolinite (solid squares), methylated quartz (solid circles), montmorillonite (open squares), hydrophobic
shale O1A (solid triangles) (OOPI signifies original oil in place).

advancing contact angle is low (10 30). However, on the [19] The observed water/oil contact angles are relevant to
reservoir rock, shown in Figure 1b, water forms a sharp capillary invasion of an initially water-saturated caprock
three-phase contact line and the advancing contact angle of above an oil reservoir. In order to use the data in a predictive
120 indicates a strongly hydrophobic, i.e., oil-wet behav- manner, a correction for the interfacial tension changes with
ior. This wetting behavior is enhanced when air is replaced temperature would have to be made [Buckley, 2001].
with oil. The solid/liquid/liquid contact angle can be small However, for screening purposes, ambient condition wa-
(e.g., 30 in Figure 1c) or very large (140 160) for crude
oil treated rocks (Figure 1d). The effect of crude oil
treatment can be very different. The crude oil forms a layer
on a hydrophobic surface and makes it even more hydro-
phobic (Figure 1d). However, in other samples, which are
hydrophilic, (e.g., L1_390 in Figure 1c) the contact angle in
air remains below 60 even after crude oil treatment. It
appears that in this case the crude oil does not form a
continuous layer due to the very different rock-oil inter-
actions. This layer is easily destroyed when the treated
surface is exposed to water. The rehydration of shale
L1_390-C was followed with optical microscopy. An in-
tensive slaking and the formation of multiple microcracks
on the shale surface were observed. The fast formation of
cracks is accompanied by a decrease in the contact angle.
The water in air contact angle on the hydrophilic shale
L1_390-C decreased from 130 after oil treatment to a 30
within few minutes only (Figure 3). In contrast, little change
in contact angle was observed on the hydrophobic shale
O1A-C (Figure 3). It seems natural, in case of light crude
oil, that a hydrophilic surface, containing polar and disso- Figure 6. Pressure curves from forced imbibition tests
ciating groups retains affinity for water even after crude oil employing a constant rate of flow of 1 mL/min from a
treatment. Tests were also performed with pure kaolinite syringe infusion pump. Dotted gray line, methylated
and a quartz-montmorillonite mixture. For kaolinite, there hydrophobic quartz; solid gray line, oil treated hydrophilic
was a small decrease in the contact angle, the later reach- shale L1_390-C; solid black line, oil treated hydrophobic
ing a higher plateau value in comparison to a less shale O1A-C. Treated shales show capillary entry pressure,
hydrophobic montmorillonite-quartz mixture (Figure 3). whereas clean quartz does not. Rapidly falling segments of
This test very clearly differentiates between samples of the curves occurred when the pump was switched off, after
varying wettability. Darcy flow was established for some time. This did not
occur with sample L1_390C.

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B07202 BORYSENKO ET AL.: WETTABILITY OF CLAYS AND SHALES
Figure 7. Time evolution of (a) dielectric constant and
(b) resistivity of shale samples: O1A-CW (open circles) and
L1_390-CW (open triangles) after initial water saturation;
O1A-CW (solid circles) and L1_390-CW (triangles) 24 h
later; quartz (solid squares) after initial injection and
unchanged 24 h later (points superposed).
ter/air contact angles are useful to distinguish shales that are
hydrophilic or hydrophobic as well as for assessing the
effect of sample treatments such as methylation or aging in
oil.
4.2. Liquid-Liquid Extraction
[20] The formation of an oil film on the surface of rocks
results in a significant reduction of the specific surface
energy and a substantial alteration of the wettability. This is
clearly seen in the liquid-liquid extraction tests presented in
Figure 4. In their natural state (before aging) montmoril-
lonite and L1_390 shale show a high affinity for water,
shale O1A, and quartz show moderately hydrophobic be-
havior with 40 50% of the particles in the water phase and
kaolinite only 10% (Figure 4a). The hydrophobicity of the
last three samples strongly increases after crude oil treat-
ment: more than 90% of the kaolin particles are extracted in
the oil phase and less then 20% of quartz and O1A shale
powder is suspended in water. The L1_390-C shale and the
montmorillonite were not permanently altered though, and
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B07202
in time reverted to a water-wet state: more than 80% of the
powder remained in the water (Figure 4b). For montmoril-
lonite, this took several hours of exposure to water. On the
contrary with kaolin, which has a higher affinity for oil, the
hydrophobicity persisted even when exposed to water
(compare Figures 4a and 4b). The present observations
are in line with previous findings [Bantignies et al., 1997;
Cosultchi et al., 2005; H. G. Rueslatten et al., A combined
use of CRYO-SEM and NMR-spectroscopy for studying the
distribution of oil an brine in sandstones, paper presented at
SPE/DOE 27804 IOR Symposium, Society of Petroleum
Engineers, Tulsa, Oklahoma, 17 20 April 1994].
4.3. Spontaneous and Forced Imbibition
[21] In hydrophilic samples, the rate of spontaneous
imbibition is high, and limited by the permeability of the
porous medium. On the other hand, if the sample is strongly
hydrophobic then very little water will enter the sample, and
consequently only a small amount of oil will be recovered.
Behavior between these two extreme limits indicates an
intermediate wetting state. In our tests the highest rate of oil
recovery during spontaneous imbibition was measured for
clean quartz followed by the most hydrophilic shale L1_390
(Figure 5). A lower spontaneous imbibition rate was found
for methylated quartz, QM, and practically no oil displace-
ment by water was observed with the hydrophobic shale
O1A-C (Figure 5). A slower oil recovery was observed with
montmorillonite in comparison with kaolin (Figure 5),
which is the opposite of the wetting behavior seen in the
liquid-liquid extraction tests (Figure 4). This difference is
attributed to the significant swelling of the montmorillonite
powder during hydration, which reduces pore and interpar-
ticle space so that both liquids become trapped [Jada et al.,
2006].
[22] Forced imbibition was used to investigate the process
of liquid penetration and interface evolution in packed
particle beds (Figure 6). The degree of hydrophobicity of
the sample can be quantified by the pressure required to
break through the capillary resistance [Al-Bazali et al.,
2008]. In the clean quartz samples, Q, the pressure profile
characteristic of a Darcy flow begins to develop on com-
mencement of water injection. That is, water immediately
enters the sample with no capillary entry pressure to
overcome. In the powdered and oil-aged shales, when water
injection commences, the pressure rises up to a certain value
from where a more gradual curve develops. For samples
L1_390-C and O1A-C we deduce that it was necessary to
overcome a capillary entry pressure of about 6 kPa and
10 kPa respectively. Thus the observed capillary entry
pressure is larger for more hydrophobic samples.
[23] After the initial injection, the pressure increases
slowly as water penetrates the pack and then reaches
saturation, with a plateau value for quartz and O1A-C shale;
that is, these samples develop a Darcy flow. In sample
L1_390-C the pressure continues to rise without reaching an
equilibrated plateau and this we attribute to a gradual
rehydration and swelling that reduces the permeability of
the packed bed.
4.4. Dielectric Measurements
[24] Two stages of water saturation were also identified
by dielectric measurements at 10 MHz (Figure 7). At low
B07202 BORYSENKO ET AL.: WETTABILITY OF CLAYS AND SHALES B07202

Figure 8. Nuclear magnetic resonance results following oil and water treatments on quartz model
system. Transverse relaxation time (T2) spectrum of (a) hydrophilic and (b) hydrophobic quartz
presaturated with oil and then rehydrated. For reference, the T2 peaks of quartz completely saturated with
oil (gray dashed line) and quartz completely saturated with water (black dashed line) are also shown.

water saturation, all samples (quartz and shales Figure 7a)
have a low dielectric constant (
10). As hydration pro-
gressed, the dielectric constant increased. The lowest di-
electric constant was found for quartz, reflecting the small
specific surface area of quartz compared with clay minerals:
the latter have surface charges that become polarized at low
frequency, contributing to the measured dielectric constant
[Cosenza and Tabbagh, 2004]. At low and moderate satu-
ration, quartz resistivity exceeds the value obtained for
shales (Figure 7b), reflecting entrapment and isolation of
the water phase by oil films.
[25] For shales, increasing water saturation results in an
increase in the dielectric constant and a monotonic decrease
in resistivity for the hydrophilic shale L1_390-CW. Water
effectively wets the surface after displacing the oil, ensuring
effective charge mobility. On the contrary, for hydrophobic
shale and quartz the resistivity decreases until the water
saturation reaches 5% (Figure 7b). Then the resistivity
essentially remains at a plateau (with a slight increase for
quartz due to polarization of oil/water interfaces in porous
space). This plateau in the resistivity indicates that in
hydrophobic shale and quartz both liquids, oil and water,
are redistributed in such a way that efficient conduction
pathways through the interaggregate pore space cannot be
established. This effect is illustrated even more strongly
when samples were kept over 24 h to allow spontaneous
liquid/liquid redistribution and equilibration within the pore
space. While the hydrophilic sample L1_390-CW shows the

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Figure 9. Nuclear magnetic resonance results following oil and water treatments on quartz-
montmorillonite model system. Transverse relaxation time (T2) spectrum after water saturation only
(gray line); after oil saturation only (gray dotted line); and following oil/water displacement from an
initially oil saturated sample following a period of rehydration (solid black line).

same decrease of resistivity (as described above), for
hydrophobic shale O1A-CW there is a significant increase
in the dielectric constant and resistivity at 5 15% of water
saturation. Thus in hydrophobic shale O1A-CW, water
becomes spontaneously displaced from the surface and
entrapped in rock pore space. During water injection both
oil and water apparently become redistributed, depending
on the rock surface wettability. This directly affects the
dielectric properties of the system and can be used for
monitoring the rock wetting behavior.
4.5. NMR Spectroscopy
[26] NMR transverse relaxation time (T2) spectra are
presented in Figure 8 for quartz particles of 150 180 mm
diameter, the pore size is typically 20 50 mm across. In this
case both oil and water are located in the large pores. The T2
distribution for quartz presaturated with oil and then grad-
ually rehydrated is essentially a superposition of the signals
obtained for each individual liquid (oil plus water). T2
distributions are different for clean quartz (Figure 8a) and
hydrophobic (methylated) quartz (Figure 8b). The water
peak is higher for the hydrophilic quartz while in the
hydrophobic sample the oil peak dominates. Therefore more
oil is displaced by water from a pore space of equivalent
geometry when the solid surface is hydrophilic.
[27] The T2 distributions acquired in the quartz-montmo-
rillonite mixture (M+Q; 90% quartz, 10% montmorillonite)
are shown in Figure 9. The light gray dotted line shows the
oil peak (104 106 ms) after oil saturation of the mineral bed.
That can be compared to water saturated sample: The T2
distribution, shown as a gray line, where distinct peaks of
clay-bound water (below 104 ms) are easily distinguished
from the water peak located within intergranular pores (T2 >
105 ms). The black line shows the T2 peak obtained after
rehydration of the oil saturated M+Q sample. The resultant
T2 is a superposition of both the oil and water peaks. At the
same time, the oil peak at T2 < 104 ms is displaced by the
water peak. In this case both liquids are bound more tightly
to the surface than in the case of coarse quartz (compare
Figures 9 and 8). Liquid/liquid displacement occurs within a
more confined pore space: the peaks are located at lower
times due to the presence of clay particles in the intergran-
ular pore space.
[28] In crude oil-treated granular shale packs exposed to
water by forced imbibition, the T2 peak of the clay-bound
water is even more distinct at T2  103 ms (Figure 10). It is
much larger for the hydrophilic sample L1_390-C (Figure 10a)
in comparison with the hydrophobic one O1A-C (Figure 10b).
In contrast, the oil peak at T2 = 104 105 ms is higher in
O1A-C. During water penetration into the crude-treated
hydrophilic shale L1_390-C (Figure 10a), the oil peak at
104 105 ms shifts to the left and decreases; at the same time
the peaks for clay-bound water (T2 < 103 ms) and interpar-
ticle pore space water (T2
105 106 ms) grow. This
probably reflects the displacement of the surface oil film
by the water. On the contrary, during water penetration into
the hydrophobic shale O1A-CW (Figure 10b), we observe
negligible growth of the oil peak (T2 = 104 105 ms). Further
water penetration was accompanied by a growth of the water
peaks at T2 > 105 ms, reflecting filling of interparticle pore
space, where water avoids the surfaces and does not cause
liquid/liquid displacement.
5. Summary
[29] Our results illustrate that shale samples are particu-
larly challenging for wettability studies due to the difficulty
in accessing the very restricted or tight pore space with
different liquids. We have focused our work on understand-
ing the fundamental interfacial phenomena before attempt-
ing direct measurements on shales in their intact state, and
in situ conditions of elevated pressure and temperature. We

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Figure 10. Nuclear magnetic resonance results following oil and water treatments on crude oil treated
shales prepared as granular packs. T2 spectrum of (a) hydrophilic sample L1_390 and (b) hydrophobic
sample O1A shale. The solid line is the sample after oil treatment only, and the dashed line is the
relaxation distribution after water injection.

approached the problem using model systems and crushed
shale particle packs to access polymineralic internal surfa-
ces, employing a range of characterization methods each of
which gives us a part of the overall picture. The sessile drop
method is a very direct measure of relative wetting tendency
but is effective for qualitative considerations only due to the
effect of surface roughness and heterogeneity. Liquid/liquid
extraction, spontaneous and forced imbibition are also
relatively simple methods and require further information
to confirm the surface properties in order that we can
interpret their outcomes reliably. We used dielectric and
NMR spectroscopy to obtain finer level information about
which fluid was preferentially wetting the surfaces within
the shale packs; the approach seems to have been validated
by the good correspondence between what we deduce from
these spectroscopic probes and what we observe in macro-
scopic measurements.
[30] We have demonstrated that mineralogically and tex-
turally distinct shales show different affinities for oil and
water, ranging from strongly hydrophilic to strongly hydro-
phobic. By comparing pure minerals and natural shales, the
influence of mineralogical structure and wettability of the
individual shale components (clay minerals and quartz) on
liquid/liquid displacement and liquid distribution inside
granular shale packs was examined.

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[31] Identifying petrophysical signatures of the prevailing
wetting state and assessing the susceptibility to wettability
alteration (e.g., by drilling fluids or during production
processes) is highly desirable for shales as well as various
reservoir lithologies. We have demonstrated that dielectric
and NMR methods, used already for reservoir rocks, are
applicable to clays and shales.
[32] Petrophysical properties were consistent with wetting
behavior and the swelling tendency of the shale minerals.
While our results from wettability assays show a highly
consistent pattern, most of our work so far has focused on a
detailed understanding of two end-member shales (L1_390
which is hydrophilic and O1A which is hydrophobic). We
now need to understand how representative these two shales
are when compared with a wider range of mudrock catego-
ries. The differences between O1A and L1_390 are not only
mineralogical: while we do believe that the kaolinitic nature
of O1A is important in its relative hydrophobicity, in line
with previous studies on reservoir rocks ([Buckley, 2001;
Zhang et al., 2000; H. G. Rueslatten et al., presented paper,
2004]), there are also substantial differences in texture, with
the L1_390 sample being extremely fine grained in its illitic
matrix and O1A being relatively silty. We are therefore
proceeding to apply our various screening methods on a
wider variety of preserved and dried shales, to confirm and
reinforce the predictive value of our results.
6. Conclusion
[33] Our most important finding is that not all shales are
the same as far as wettability is concerned. There is a
significant variation in surface affinity for oil versus water,
as determined by particle partition experiments, contact
angle measurements on intact samples and a wide range
of porous pack experiments on crushed samples. Initial
correlations suggest that hydrophilic shales have a higher
surface activity (surface charge density and specific area,
combining to produce higher CEC), and that illitic and
smectitic mudrocks are more hydrophilic whereas kaolinitic
mudrocks are potentially hydrophobic, being wet preferen-
tially by oil and retaining that tendency after hydration. The
direct observations using optical and fluorescence micros-
copy as well as low vacuum SEM confirmed our interpre-
tations of the petrophysical responses (NMR and dielectric)
concerning those shales which are hydrophilic and chose
which have a tendency to adsorb oil and even become oil
wet. The petrophysical findings and microscopic observa-
tions are consistent with the measurements of the wetting
and swelling tendencies of the powders and intact shales.
[34] Acknowledgments. This paper is a contribution to the Joint
Industry Project Integrated Predictive Evaluation of Traps and Seals
(IPETS). We thank the sponsors Chevron, Woodside, Santos, Origin,
Anadarko, PIRSA, and Schlumberger for their support and permission to
publish. The participation of Woodside and Chevron is through the Western
Australian Energy Research Alliance. The Wealth from Oceans National
Research Flagship is thanked for substantial financial coinvestment in the
project. Origin Energy and the Geological Survey of Western Australia are
thanked for the provision of the preserved shales cores used in the study.
Finally, support from the ARC linkage scheme is gratefully acknowledged.
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A. Borysenko, J. Ralston, and R. Sedev, Ian Wark Research Institute,
University of South Australia, Mawson Lakes, SA 5095, Australia.
(rossen.sedev@unisa.edu.au)
I. Burgar, CSIRO Materials Science and Engineering, Clayton South, Vic
3169, Australia.
B. Clennell, D. Dewhurst, and K. Liu, CSIRO Petroleum, 26 Dick Perry
Avenue, Kensington, WA 6151, Australia.
M. Raven, CSIRO Land and Water, Waite Road, Urrbrae, SA 5064,
Australia.