Advances in Water Resources 97 (2016) 279–298

Contents lists available at ScienceDirect

Advances in Water Resources

journal homepage: www.elsevier.com/locate/advwatres

In-situ characterization of wettability and pore-scale displacements

during two- and three-phase flow in natural porous media
M. Khishvand, A.H. Alizadeh∗, M. Piri
Department of Petroleum Engineering, University of Wyoming, Laramie, WY 82071-2000, USA

a r t i c l e i n f o a b s t r a c t

Article history: We establish a unique approach to measure in-situ contact angle from micro-CT images acquired during
Received 2 March 2016 two- and three-phase miniature core-flooding experiments in order to overcome the uncertainties asso-
Revised 7 October 2016
ciated with conventional contact angle measurement techniques. The measurements are used to quantify
Accepted 7 October 2016
the wettability behavior of the rock and explain pore-level displacement events occurring in three-phase
Available online 8 October 2016
flow. Six two-phase experiments are performed on individual core samples with three pairs of fluids, i.e.,
Keywords: oil-brine, gas-oil, and gas-brine, and under two thermodynamic conditions: (a) binary-equilibrated, when
Pore-scale contact angle only the two respective phases are at equilibrium and (b) ternary-equilibrated, when all three phases are
Two-and three-phase flow equilibrated and only the two desired fluids are injected into the core. A three-phase experiment set is
Hysteresis also performed under ternary-equilibrated conditions, which includes gas injection, a waterflood, and an
Double displacement oilflood process. All experiments are performed on Berea miniature core samples using a nonspreading
Micro-CT imaging
brine-oil-gas fluid system.
We measure receding and advancing contact angles at arc menisci and main terminal menisci for the
two-phase binary-equilibrated experiments and characterize contact angle hysteresis for each fluid pair.
Contact angle hysteresis values are almost identical for all fluid pairs. The results of the two-phase binary-
and ternary-equilibrated experiments show similar contact angle distributions for each fluid pair. Contact
angle distributions during the three-phase flow experiment are analyzed to develop new insights into rel-
evant complex displacement mechanisms. The results indicate that, during gas injection, the majority of
displacements involving oil and water are oil-to-water events. It is observed that, during the waterflood,
both oil-to-gas and gas-to-oil displacement events take place. However, the relative frequency of the for-
mer is greater. For the oilflood, gas-water interfaces only slightly hinge in pore elements. Pore-scale fluid
occupancy maps and the Bartell–Osterhoff constraint verify the above-mentioned findings.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction property through some measurable parameters, such as contact an-

Among all factors affecting multiphase flow in porous media,
wettability undoubtedly plays a key role. It is a manifestation of
complex rock-fluid interactions and has a significant impact on
the microscopic distribution of fluid phases and fluid-fluid inter-
face movement in the pore space. Wettability substantially influ-
ences multiphase flow properties, such as remaining oil satura-
tion, relative permeability, and capillary pressure (Alizadeh and
Piri, 2014b; Anderson, 1986a; Hirasaki, 1991; Morrow, 1990; Mor-
row and Nguyen, 1982; Zhou and Blunt, 1998). The fact that wet-
tability of oil reservoirs can fall into a broad wetting spectrum
ranging from strongly water-wet to strongly oil-wet (Cuiec, 1984;
Treiber et al., 1972) motivated researchers to quantify this surface
∗
Corresponding author.
E-mail address: aalizade@uwyo.edu (A.H. Alizadeh).
gle. Contact angle is the most universal and accepted measure of
the wettability of a surface (Morrow, 1990) and is determined at
the contact line where three phases (i.e., two fluids and the solid)
meet. By convention, it is measured through the denser fluid.
Although various techniques, such as sessile drop, captive bub-
ble, and dynamic Wilhelmy plate (Buckley, 2001), have been pro-
posed over the years to measure the contact angle, they all suf-
fer from some drawbacks. Perhaps, the main common drawback
of these methods is the selection of the solid surface. This arises
from the fact that all contact angle measurements, even at reser-
voir conditions and with reservoir fluids, are made on smooth,
flat, and pure surfaces (Anderson, 1986b). While the selection of
the substrate is based on the predominant mineral component of
the reservoir rock, e.g., quartz as a representative of sandstones,
this approach may not consider the mineral heterogeneities ob-
served in the pore space even in a single pore element. In other

http://dx.doi.org/10.1016/j.advwatres.2016.10.009
0309-1708/© 2016 Elsevier Ltd. All rights reserved.
280 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
Nomenclature
Cso spreading coefficient of oil on water in the presence
of gas
FOV field of view
IFT interfacial tension
K permeability
SGI secondary gas injection
SP saturation point
Greek letters
γ interfacial tension
θ contact angle
φ porosity
Subscripts
abs absolute
a advancing
g gas
h hinging
o oil
r receding
w water (brine)
Superscripts
AM arc meniscus
eq equilibrium
i initial
MTM main terminal meniscus
words, in mineralogically complex systems such as natural rocks,
the minerals lining the pore walls and their distributions may vary
from one location to another, leading to different wetting proper-
ties (Morrow, 1990). This, however, is overlooked in conventional
laboratory measurements of contact angle. Additionally, the sub-
strates used for contact angle measurements have smooth sur-
faces whereas the pore walls in natural rocks have microscopic
roughness – one of the main reasons causing contact angle hys-
teresis (Israelachvili, 2011; Morrow, 1975; Oliver et al., 1980), the
difference between advancing contact angle (when the wetting
phase displaces the non-wetting phase) and receding contact angle
(when the non-wetting phase displaces the wetting phase). Fur-
thermore, the substrates used in these measurements have flat sur-
faces, while pores are often formed with curved walls. Curvature of
the solid surface may significantly impact contact angle measure-
ments. All the above-mentioned drawbacks imply that contact an-
gle measurements made through conventional techniques may not
precisely represent the wetting characteristics of natural rocks, un-
less made directly inside the pore space under relevant conditions.
This goal, however, was unattainable for many years.
The advent of imaging techniques, in particular X-ray com-
puted tomography, in the past few decades has created a turn-
ing point for fundamental studies in environmental engineering
and petroleum engineering. The use of X-ray computed tomogra-
phy (CT) to determine physical and chemical properties of porous
media and their fluid contents with spatial resolutions on the sub-
millimeter (micron) level has created invaluable opportunities to
develop insights into fundamentals of fluid flow through porous
media. This novel technology enables us to visualize spatial dis-
tribution of fluids at the pore level by means of miniature core-
flooding setups and micro-CT scanners (Alizadeh et al., 2014). The
use of micro-CT imaging is increasingly becoming pervasive in var-
ious areas of reservoir engineering, such as pore-scale character-
izations (Arns et al., 2005), investigation of trapped non-wetting
phase clusters (Iglauer et al., 2010; Khishvand et al., 2016), vi-
sualization of fluid occupancy in fractures (Karpyn et al., 2007),
and capillary pressure characterization (Armstrong et al., 2012).
Wildenschild and Sheppard (2013) have provided more details re-
garding the applications of X-Ray microtomography. Micro-CT im-
ages have recently also been used to measure contact angle at the
pore level (Andrew et al., 2014; Khishvand et al., 2016). Andrew
et al. (2014) carried out a flow experiment on Kenton limestone us-
ing a supercritical CO2 -brine fluid system and measured pore-scale
contact angles at the end of imbibition using X-ray microtomog-
raphy. The measured contact angles covered a range of values (a
distribution), which was ascribed to contact angle hysteresis and
surface heterogeneity. Optical thin section and SEM images were
used to examine surface roughness. No attempt was made to dis-
cern the difference between hinging and advancing contact angles.
Measurement uncertainties (particularly voxelation error) and con-
tact angle relaxation due to the cessation of flow prior to scanning
could have influenced the results. During relaxation, as the system
is allowed to come to rest, the advancing (or receding) angle may
approach toward an equilibrium value (Bartell and Merrill, 1932;
Hassanizadeh and Gray, 1993). Khishvand et al. (2016) addressed
some of these uncertainties and improved wettability characteriza-
tion techniques during their measurements on Gambier limestone
and Bentheimer sandstone. To avoid contact angle (interface) relax-
ation, flow of fluids was not stopped while scanning. All the con-
tact angles were measured at steady state. They used a new seg-
mentation approach (and adequate phase contrasts) instead of con-
ventional watershed segmentation to minimize the voxelation er-
ror. It was also tried to distinguish between Main Terminal Menis-
cus (MTM) and Arc Meniscus (AM) contact angles and characterize
receding and advancing angles during drainage and imbibition pro-
cesses. The investigators employed their technique to measure in-
situ oil-brine contact angles and used the data to explain capillary
de-saturation behavior of different rock samples. In the present
study, we used a similar technique to characterize contact angle
distributions for three different pairs of fluids and then employed
the measurements to develop an improved insight into subtle com-
plexities of pore-scale displacement mechanisms during two- and
three-phase flow processes that had only been proposed theoret-
ically and not been examined experimentally at the pore scale in
natural porous media.
We performed two- and three-phase flow experiments on Berea
sandstone rock samples and imaged fluid configurations inside the
pore space to measure contact angles at arc menisci and main
terminal menisci. This study was aimed at establishing a supe-
rior workflow, which could overcome some of the errors associated
with conventional contact angle measurement techniques, such as
overlooking mineral heterogeneity and surface roughness. We pro-
vided a perfect framework including a robust experimental pro-
cedure and a comprehensive image analysis approach to quantify
the wettability behavior of the rock during two- and three-phase
flow experiments. We evaluated the effect of relaxation on the
interface movement and highlighted the importance of continu-
ous flow during in-situ contact angle measurement. For the first
time, in-situ receding, hinging, and advancing contact angle dis-
tributions were characterized for different pairs of fluids, i.e., oil-
brine, gas-oil, and gas-water, in a natural rock. These values are
representative of the wettability behavior of Berea sandstone. We
also explained displacement mechanisms responsible for the ob-
served contact angle trends. Moreover, a series of two-phase oil-
brine, gas-oil, and gas-brine experiments were performed under
different thermodynamic conditions to examine the effect of fluid
equilibration on contact angle behavior. Finally, we conducted a
three-phase flow experiment to determine contact angle distribu-
tions and use them, along with pore-scale images, to find domi-
nant double displacement mechanisms occurring during the three-
phase saturation path taken in the experiment.
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 281

Table 1 Table 2
Geometrical and petrophysical properties of the core samples used in the ex- Physical properties of the fluids used in the experiments.
periments.
Densitya Viscosityb Interfacial Tensiona
Experiment Length Diameter φ X−ray Kliquid
abs
a
Pore volume (kg/m3 ) (mPa.s) (mN/m)
(mm) (mm) (fraction) (mD) (cm3 )
Brine (200g/l NaI + 15g/l CaCl2 ) 1102 1.08 –
A 80 4.60 0.206 592.54 0.274 Oil (decalin + 5vol% idooctane) 843 2.5 –
B 78 4.80 0.207 558.38 0.293 Gas (N2 ) 25.9 0.019 –
C 79 4.85 0.212 551.58 0.312 Oil-Brine – – 45.16
D 77 4.45 0.211 590.03 0.253 Gas-Oil – – 26.61
E 81 4.61 0.220 561.76 0.297 Gas-Brine – – 66.73
F 80 4.82 0.204 541.23 0.296 a
Density and IFT values were measured at 5.52 MPa and ambient temperature
G 81 4.47 0.196 584.46 0.249
when all three fluids were equilibrated before using the desired fluids
a
Kliquid
abs
was measured with oil for Samples B and E and with brine for the b
Measured at 0.1 MPa and ambient temperature.
rest.

equilibrium at experimental conditions, i.e., 5.52 MPa and 20 °C.

2. Experiments The values are reported in Table 2 and were used to calculate
the equilibrium spreading coefficient using the following equation
Six sets of two-phase and one set of three-phase flow exper- (Adamson, 1990):
iments were conducted on vertically oriented core samples using
a brine/oil/gas fluid system at ambient temperature and 5.52 MPa
eq
Cso = γgw
eq
− (γgo
eq
+ γow
eq
) (1)
where γgw , γgo , and γow are gas-water, gas-oil, and oil-water equi-
back pressure. Each experiment was performed on an individual eq eq eq

sample. A net overburden pressure of 0.69 MPa was applied dur- eq

ing all experiments. The two-phase experiments were performed
with oil-brine, gas-oil, and gas-brine fluid pairs under two ther-
modynamic conditions: (a) binary-equilibrated, when only the two
respective phases were at equilibrium (Experiments A, B, and C)
and (b) ternary-equilibrated, when all three phases were at equi-
librium (Experiments D, E, and F). For the three-phase experiment
(Experiment G), all three phases were equilibrated at the experi-
mental conditions as well prior to the experiment.
2.1. Rock and fluid properties
librium IFT values, respectively, and Cso denotes the equilibrium
spreading coefficient. The equilibrium spreading coefficient cal-
culated using the measured interfacial tension values was -5.04
mN/m indicating that decalin was nonspreading in our fluid sys-
tem. The nonspreading behavior implies that the oil phase forms
lenses with definite angle at the gas-water interface between brine
in the corner(s) and gas in the center. It also means that oil will
have much less tendency to spread in the pore spaces.
In the rock-fluid system selected, the aqueous, oil, and gas
phases were considered as the wetting, the intermediate-wetting,
and the nonwetting phases, respectively.

Seven miniature core samples were cut from a block of Berea
sandstone using tap water as a coolant, dried in an oven at 110 °C
for one day, and then stored in a desiccator. No cleaning with sol-
vents was made before/after the experiments. The diameter and
the length of the cores (Samples A to G) varied from 4.45 to
4.85 mm and from 77 to 81 mm, respectively. Porosity distri-
bution determined using X-ray imaging along fields of view (i.e.,
scanned sections of the core samples) were uniform indicating that
the mediums were homogeneous. Fig. S1 in Supplementary mate-
rial shows an example of the porosity distribution for Sample B.
The porosity of the samples varied between 0.196 and 0.220. Ab-
solute permeability to the wetting phase was measured for each
core sample at the outset of the experiment under 0.69 MPa pore
pressure and 0.69 MPa net overburden pressure. Since the samples
had been cut from the same block, their absolute permeabilities
fell within a narrow range (approximately from 541 to 593 mD).
Table 1 lists geometrical and petrophysical properties of all core
samples used in the experiments.
The aqueous phase was prepared by dissolving 200 g NaI and
15 g CaCl2 in one liter of distilled water. The oil phase was com-
posed of decalin and 5 vol% iodooctane. The X-ray dopants, i.e.,
sodium iodide and iodooctane, were added to the liquids in or-
der to better distinguish the phases. The concentrations selected
provided sufficient contrasts for the purpose of segmentation. All
chemicals were reagent grade and used as received. Brine was de-
gassed for about 15 min before use. Commercial nitrogen was used
as the gas phase. The fluid and fluid-fluid properties were mea-
sured at experimental conditions and are listed in Table 2. The
aqueous and oil phases are hereafter referred to as water and oil,
unless stated otherwise.
Interfacial tension (IFT) was measured for each pair of flu-
ids using the Axisymmetric Drop Shape Analysis technique (Saraji
et al., 2013), while all three phases had already been brought into
2.2. Experimental apparatus
The flow experiments were conducted using a state-of-the-art
experimental apparatus, which included a reservoir-condition core-
flooding setup integrated with a high-resolution micro-CT scanner.
The apparatus was designed to study multiphase flow and relevant
displacement physics at the pore scale.
The core-flooding setup was a closed-loop system composed
of six dual-cylinder QuizixTM pumps, a miniature custom-built core
holder made out of carbon fiber, RosemountTM differential pressure
transducers, a three-phase separator, compensation accumulators,
and a mechanical convection oven. Fig. S2 in Supplementary mate-
rial shows a detailed schematic diagram of the setup. All parts of
the apparatus exposed to fluids were made out of HastelloyTM or
other corrosion-resistant materials. To conduct flow experiments
on small samples under confining pressure, we designed and built
miniature core holders with various dimensions. The pumps were
used for fluid (e.g., oil, gas, and water) injection, back pressure
regulation, overburden pressure maintenance, and separator pres-
sure regulation. The fluids were injected from the bottom of the
core samples at constant flow rates and received from the top
at constant pressure. The injection pumps withdrew their respec-
tive fluids for reinjection into the core sample from the separa-
tor, whereas the back pressure regulation pump discharged its con-
tents, i.e., the effluents received from the core, into the separator.
All positive or negative mass accumulations in the separator (due
to retraction/injection of fluids from/into the separator) were com-
pensated by a pressure regulation module, resulting in a very sta-
ble separator pressure. Stability of the separator pressure insured
that the thermodynamic equilibrium between the phases would
be maintained in the course of an experiment. More details of the
core-flooding setup can be found elsewhere (Alizadeh et al., 2011;
Alizadeh and Piri, 2014a).
282 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298

Table 3
Flow rates, saturation data, capillary numbers, and test duration for end points of the two-phase experiments and all stages of the three-
phase experiment performed in this study.

Experiment Step Brine Oil Gas Brine Oil Gas Capillary Test
flow rate flow rate flow rate saturation saturation saturation number duration
(cc/min) (cc/min) (cc/min) (fraction) (fraction) (fraction) (days)

A Drainage 0 0.015 0 0.36 0.64 0 1.29E−07 1

Imbibition 0.02 0 0 0.55 0.45 0 7.44E−08 3
B Drainage 0 0 1.2 0 0.35 0.65 1.22E−07 1
Imbibition 0 0.003 0 0 0.63 0.37 4.02E−08 3
C Drainage 0 0 0.3 0.36 0 0.64 1.19E−08 1
Imbibition 0.03 0 0 0.57 0 0.43 6.79E−08 3
D Drainage 0 0.015 0 0.36 0.64 0 1.38E−07 1
Imbibition 0.02 0 0 0.57 0.43 0 7.94E−08 3
E Drainage 0 0 1.2 0 0.36 0.64 1.33E−07 1
Imbibition 0 0.003 0 0 0.64 0.36 4.36E−08 3
F Drainage 0 0 0.3 0.34 0 0.66 1.21E−08 1
Imbibition 0.03 0 0 0.57 0 0.43 6.87E−08 3
G Oil drainage 0.01 0.009 0 0.53 0.47 0.00 8.20E−08 0.5
Gas injection 0.001 0.0 0 09 0.09 0.35 0.27 0.38 1.06E−08 1
Waterflood 0.001 0.0 0 03 0.03 0.47 0.20 0.33 3.94E−09 1
Oilflood 0.001 0.0 0 09 0.03 0.42 0.26 0.32 1.39E−08 1

The X-ray imaging system was a VERSA-XRM500 micro-CT
scanner manufactured by Zeiss. The equipment had a stage on
which the core holder was vertically mounted between the source
and the detector and could scan various sample sizes with a range
of resolutions up to 700 nm. We endeavored to minimize undesir-
able vibrations/torque on the core holder during the stage rotation
(shift) by using high-pressure flexible tubing connecting the core
holder to the flow system. The shift control played an important
role in reducing artifacts as well as improving the image quality.
2.3. Experimental procedure
To start an experiment, the sample was placed in the core
holder under confining pressure, and a reference dry scan was ob-
tained. Subsequently, the core was flooded with gaseous CO2 to
remove air and then vacuum saturated with the wetting phase
(water or oil). A monitoring scan (with a resolution of 4.36 μm)
was conducted to insure that the core was fully saturated with the
wetting phase. To establish initial wetting phase saturation during
the two-phase flow experiments, the nonwetting phase was in-
jected into the core by increasing its flow rate incrementally. Af-
ter establishing the desired initial wetting phase saturation, the
two-phase experiment was followed by an imbibition process un-
der the capillary-dominated flow regime (i.e., the capillary num-
ber (Khishvand et al., 2016) was in the order of 10−6 ). Unlike the
drainage steps, which were carried out only by injecting the non-
wetting phase (the unsteady-state approach), both the wetting and
nonwetting phases were simultaneously injected during the im-
bibition steps (the steady-state approach) in order to have a bet-
ter control on the intermediate saturation points (before reaching
trapped nonwetting phase saturation) where some of the contact
angle measurements were intended to be made. The imbibition
process during each two-phase experiment was continued to es-
tablish residual nonwetting phase saturation. Table 3 summaries
flow rates, saturation data, capillary numbers, and test duration for
the end points of the two-phase experiments.
Contact angle was determined in both drainage and imbibi-
tion steps of the two-phase experiments. During drainage, contact
angles were measured at one saturation point (SP) after partial
oil drainage (i.e., before reaching initial wetting phase saturation)
whereas, during imbibition, they were measured at three satura-
tion points including two intermediate points where both phases
were mobile and one at residual nonwetting phase saturation.
To determine the values of contact angles, the center part of the
core samples were scanned at stable conditions, that is, the fluid
configurations no longer changed at a given set of flow rates. This
was identified by monitoring scans performed every two hours.
The monitoring scans were usually started after injecting a large
number of pore volumes. After the stability check, the main scan
was conducted at a resolution of 1.5 μm for contact angle mea-
surement. Injection of fluids was not stopped during scanning. In
some cases, we imaged the core samples at a resolution of 2.34 μm
for the purpose of saturation determination (e.g., during the three-
phase experiment). Table 4 lists microtomography parameters used
to image the samples during the experiments. Each set of parame-
ters used to conduct a specific type of scan (for instance, monitor-
ing) was stored as a recipe and called when needed.
For the three-phase experiment (Experiment G), the water-
saturated core sample was subjected to partial oil drainage fol-
lowed by gas injection, a waterflood, and then an oilflood. All se-
quences of this experiment were conducted using the steady-state
approach, and all phases were mobile in the course of each step
(see Table 3). The scanning procedure was the same as the two-
phase experiments.
3. Image analysis
Image acquisition for the contact angle scans was started after
the stability check during each flow stage. Once a recipe was exe-
cuted, the scanner took tomography projections, which were then
reconstructed to create a txm (stacked slices) file for image anal-
ysis. Each image set (i.e., txm file) was then analyzed using Avi-
zoFire software developed by FEI Visualization Sciences Group. A
customized DELLTM workstation with a 16 × 3.1 GHz processor and
a 16 × 16GB RAM was employed to accelerate the data processing
step.
The structure of image analysis in our study had two princi-
pal steps: (a) segmentation of gray-scale wet (flooded) images (ob-
tained during drainage and imbibition) using dry reference images
and (b) quantification of the segmented images to determine con-
tact angles. To start segmentation, all data sets were filtered using
the Non-Local Means filter. This module removed random noises,
increased the signal to noise ratio, and enhanced the contrast be-
tween different phases in the intensity histogram (as seen in Figs.
S3(a) and S3(b) in Supplementary material). Fig. 1(a) shows a sec-
tion of the filtered dry reference image of Sample 1 obtained with
a resolution of 1.5 μm. The segmentation process was followed
by extracting the pore space and the solid from the dry reference
image using the histogram-thresholding method (Sanei and Fertig,
2015). In this method, a lower and an upper limit was defined for
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 283

Table 4
X-ray microtomography parameters used in different imaging recipes during the experiments.

Recipe type Diameter of Length of Number of Resolution Acquisition

FOV (mm) FOV (mm) projections (x, y, z) (μm) time (hours)

Monitoring scan 4.36 3.93 1600 4.36, 4.36, 4.36 1.2

Contact angle scan 3.02 2.57 30 0 0 1.5, 1.5, 1.5 8
Saturation scan 4.68 3.98 3200 2.34, 2.34, 2.34 4

Fig. 1. Image processing workflow for a rectangular section (906 × 856.5 μm2 ) of wet and dry images taken during an imbibition process: (a) filtered dry reference image;
(b) bimodal intensity histogram of the filtered dry image with 1024 bins; (c) pore map obtained from the filtered dry image using binary histogram-thresholding; (d)
combined wet image, i.e., the wet image after registration, translation, and combination with the pore map. In this image, brine, gas, and the solid are light gray, dark gray,
and black, respectively; (e) segmented wet image obtained from segmentation of the combined wet image (brine:blue, gas:red, and grains:gray); (f) individual trapped gas
globule surrounded by brine and the solid; (g) fluid-solid-fluid contact lines passing throw triple contact points; (h) Plane X drawn perpendicular to the contact line at Point
A; and (i) contact angle determined at Point A in Plane X (resolution = 1.5 μm). (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
284 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
each phase, and all voxels with attenuation values (intensities) be-
tween the limits were assigned to that specific phase. The thresh-
old values for pores and the solid were obtained from intensity
histograms such as the one shown in Fig. 1(b). The sharp bimodal
histogram clearly supports the accuracy of the segmentation and
is an indication of sufficient phase contrasts. The outcome of this
step, called pore map (Fig. 1(c)), was used for porosity analysis as
well as segmentation of the wet images.
Thereafter, we registered and aligned each set of the wet im-
ages with its corresponding dry reference image and combined
the pore map with the wet image as observed in Fig. 1(d). The
combined image contained only fluid phases with enough phase
contrast(s) to be distinguished. Figs. S3(c)–(f) confirms sufficient
contrasts between the intensities of different fluid phases in the
combined wet images (fluid phase images). The process was then
continued by differentiating the fluid phases in the combined im-
age using the minimum points of the intensity histogram as the
threshold values, and producing a final segmented image for each
wet case; as an example, see Fig. 1(e). The segmented file in
Fig. 1(e) was analyzed to measure contact angles.
To measure contact angles, a sub-volume containing desired
fluid phases and the solid was first extracted. Fig. 1(f) exhibits
an exemplary sub-volume where an individual trapped gas glob-
ule was surrounded by water at the end of an imbibition process.
Subsequently, we visualized fluid-solid-fluid contact points to cre-
ate triple contact lines (Fig. 1(g)). To determine contact angle at
a given point on a triple contact line, e.g., Point A in Fig. 1(h), a
plane was plotted perpendicular to the triple contact line at that
point (Plain X in Fig. 1(h)). To plot the plane, we first determined
a (unique) vector tangent to the triple contact line at Point A,
which in fact is normal to Plane X at Point A. The normal vec-
tor and the coordination of Point A defined the unique perpen-
dicular plane (Plane X in this case). We then smoothed the sur-
face of the plane using a texture-interpolation method to remove
edges of the pixels. The smoothing module implemented a filter
to change the scalar data, preserve strong edges, and enhance the
contrast of edges. Finally, we traced fluid-solid and fluid-fluid tan-
gents and measured contact angle at the intersection of the tan-
gents (Fig. 1(i)).
Image analysis, particularly segmentation, is a subjective pro-
cess and its accuracy may dramatically affect the results of micro-
CT based experiments. This is even more critical when identifying
fluid-fluid and rock-fluid interfaces to characterize contact angles.
Therefore, before using any approach for image analysis, one needs
to check the accuracy and quantify possible uncertainties. To eval-
uate the accuracy of our image analysis technique and quantify the
associated uncertainties, we compared contact angles measured on
an identical plane using gray-scale (i.e., raw data) and segmented
images (Khishvand et al., 2016). The results showed consistent val-
ues with an absolute error value of about 1 ° that was considered
negligible. The small error in this case testifies the accuracy of our
segmentation method and means that our technique succeeded to
appropriately determine fluid-fluid and rock-fluid interfaces.
4. Results and discussion
Contact angles were measured under two- and three-phase
flow conditions. For two-phase flow, each pair of fluids was used
to conduct two experiments; one experiment when only the two
respective fluids were equilibrated prior to use and the other ex-
periment when all three fluids were equilibrated before using the
two desired fluids. For three-phase flow, all three fluids were at
equilibrium before use. In each experiment, contact angle measure-
ments were made for both types of interfaces: (a) Main Terminal
Meniscus (MTM) and (b) Arc Meniscus (AM). Main Terminal Menis-
cus is the invading interface at the pore-throat junction separating
the wetting and nonwetting phases, whereas Arc Meniscus (AM) is
the interface between the two phases in a corner of a noncircular
element (Mason and Morrow, 1987; 1991; Mason et al., 1988).
Core-flooding experiments are usually performed under either
constant-flow-rate or constant-pressure mode. In either approach,
the inlet pressure is always higher than the outlet pressure al-
lowing fluids to flow through the pore space. It has been argued
in the literature (Andrew et al., 2014; Bartell and Merrill, 1932;
Hassanizadeh and Gray, 1993) that when flow is stopped (i.e., the
system is let come to rest), advancing (or receding) contact angle
decreases (or increases) to reach an equilibrium value. In a core-
flooding experiment when all injection and back pressure pumps
are ceased, pressure gradient along the sample gradually becomes
zero. As a result, phase pressures across the core sample readjust
and local pressures of the fluids decreases and increases close to
the inlet and outlet ends, respectively. Thus, for the case of dis-
placing the nonwetting phase with the wetting phase for example,
when the flow of the wetting phase is stopped, the hinging con-
tact angles decrease close to the inlet and increase close to the
outlet. If an angle has already reached its advancing value, it de-
creases toward an equilibrium value when it is located close to the
inlet or maintains its advancing value when it is close to the out-
let while the fluid-fluid interface moves due to the increase in the
wetting-phase pressure. To examine the relaxation phenomenon
and changes in fluid-fluid interfaces, the flow was stopped during
a two-phase oil-displacing-water process. Images taken before and
after cessation of the flow are shown in Fig. S4 in Supplementary
material . As observed, the images confirm the above-mentioned
discussion that when the flow is stopped, the fluid-fluid interface
may stay unchanged Figs. S4(a) and S4(b) in Supplementary ma-
terial) or contact angle moves toward an equilibrium value Figs.
S4(c) and S4(d) in Supplementary material). In some cases, relax-
ation may also cause snap-off Figs. S4(e) and S4(f) in Supplemen-
tary material) as a result of interface movement.
The use of small core samples in micro-scale experiments en-
ables us to capture high-resolution images and improve the signal
to noise ratio for the analysis steps. However, it raises the question
of whether a micro-scale sample can represent all properties of the
rock being studied and exhibit the same flow behavior (such as
trapping history and capillary pressure characteristics) as a macro-
scale sample. To answer this question, we evaluated variations of
porosity and saturation (during drainage and imbibition) with the
sample volume analyzed for a given specimen. This allowed us to
determine Representative Elementary Volume (REV) for each of the
variables. To this end, a small cubic sub-volume was selected and
the aforementioned variables were determined within this volume.
The sub-volume was then incrementally enlarged, and the values
were recalculated until we reached the inscribed cube in the field
of view (FOV). Plotting the calculated porosity and oil saturation
values versus the cube volumes for Sample A in Fig. S5 in Supple-
mentary material, reveals that, for both porosity and oil saturation,
the FOV is large enough to be considered as an REV, and there-
fore the micro-scale experimental results are representative of the
core-scale values.
4.1. Protocol for contact angle measurements
We attempted to differentiate between AM and MTM contact
angles during the measurements by visual inspection of the loca-
tion of fluid-fluid interfaces spatially. If the interface was located
at a corner, for example Fig. 2(a), the measured value at the triple
contact point (here Point A) was considered as an AM contact an-
gle; if the interface was at the center of a pore-throat junction,
the measured value represented an MTM contact angle (Point B in
Fig. 2(c)).
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 285

Fig. 2. Contact angle measurements for both types of fluid-fluid interfaces during water imbibition in Sample A: (a) an AM interface in a corner of an element. Point A is
located on the triple contact line (yellow lines) where the two fluids and the solid meet; (b) the AM contact angle measured at Point A; (c) an MTM interface at the pore-
throat junction. Point B is located on the triple contact line; and (d) the MTM contact angle measured at Point B (resolution = 1.5 μm; brine:blue, oil:red, and grains:gray).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

When the nonwetting phase displaces the wetting phase
(drainage), all receding contact angles, including AM’s and MTM’s,
must be identical if the solid surface is truly smooth and miner-
alogically homogeneous. However, pore walls in naturally occur-
ring rocks are neither smooth nor mineralogically homogeneous;
therefore, the receding contact angles show some scatter meaning
that we have a distribution of receding contact angles. This is also
true for advancing AM and MTM contact angles when the wetting
phase displaces the nonwetting phase (imbibition).
If we assume that the wetting characteristics of the solid sur-
face are not altered during displacements, as assumed in this study
because we used pure fluids, receding and advancing contact an-
gles may still exhibit some differences as a consequence of sur-
face roughness. When the displacement is switched from drainage
to imbibition, the contact point may be pinned to the solid re-
sulting in hinging (increasing in) the contact angle and decreas-
ing the curvature of the fluid-fluid interface before the interface
moves. The contact angle hinges until it reaches the advancing
value where the fluid-fluid interface starts moving. Fig. 3 exem-
plifies how the receding contact angle at the end of drainage (see
Point A) starts hinging during imbibition. Point B indicates the in-
terface movement after the angle has reached the advancing value.
While moving, the fluid-fluid interface maintains its angle with the
solid surface, but its curvature may change due to changes in the
pore space if interface velocity and surface characteristics remain
the same.
Below, we first present the results of the two-phase flow ex-
periments for all three pairs of fluids before and after equilibra-
286 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
(a)
Point A
Point B
(b)
Point A
Point B
(c)
Fig. 3. Contact angles and fluid-fluid interfaces during drainage and imbibition pro-
cesses in Sample A (resolution = 1.5 μm; brine:blue, oil:red, and grains:gray). At the
end of drainage (image (a)), all contact angles are at their receding values. Point A
in image (a) shows a triple contact point. During imbibition, the contact angles start
hinging before interfaces move. The contact angle at Point A has hinged in image
(b). Point B in images (b) and (c) exhibits the movement of an interface after its
contact angle has reached the advancing value. (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this
article.)
tion with the third phase and then discuss the trends observed.
As mentioned in the experimental procedure for two-phase flow,
receding MTM and AM contact angles were measured at one sat-
uration point (Saturation Point 1 during drainage), whereas hing-
ing and advancing AM and MTM contact angles were measured
at three saturation points, two points (Saturation Points 1 and 2
during imbibition) when both phases were mobile and one point
(Saturation Point 3 during imbibition) when the nonwetting phase
was at residual saturation. For the three-phase flow experiment,
we examined the relation among the three contact angles when
the three phases were mobile and in thermodynamic equilibrium.
For each specific contact angle, several measurements were made
at random sites and a distribution was generated. As a result, the
values were considered to be unbiased and representative of the
rock-fluid system used.
4.2. Two-phase flow
4.2.1. Binary-equilibrated experiments
To perform Experiments A (oil-water), B (gas-oil), and C (gas-
water), the two desired fluids were equilibrated in the separator
(in the absence of the third phase) at the experimental conditions
for one day. For the case of the oil-water system, it was practically
impossible to maintain the pressure of the equilibration cell while
the water and oil pumps were retracting their respective fluids be-
cause both fluids were incompressible. Therefore, we depressurized
the cell very gradually after equilibration to atmospheric pressure,
filled up the water and oil pumps, and then re-pressurized wa-
ter and oil in the pumps to the experimental pressure in order to
conduct Experiment A. It was assumed that the depressurization
would not affect the equilibration between water and oil as they
were virtually immiscible. In the cases where gas was present in
the separator, compressibility of the gas allowed us to control pres-
sure variations in the separator occurring due to retraction from
and/or injection into it.
After saturating the core sample with the wetting phase (for
example, oil in the case of gas-oil system), the nonwetting phase
(gas for the gas-oil system) was injected into the sample while
its flow rate was incrementally increased resulting in increases
in gas-oil capillary pressure. When the capillary pressure reaches
the threshold capillary pressure of a pore element, the nonwet-
ting phase staying at the entrance of the element invades that
element and displaces the wetting phase. The nonwetting phase
advances through the pore space and invades the pore elements
one after the other based on their threshold capillary pressures
(the capillary-dominated regime). During this displacement, the in-
vading interface, which is an MTM, moves through the element
with a given contact angle (receding angle) while adjusting its
curvature to compensate for variations in the pore geometry (Al-
Gharbi and Blunt, 2005). Due to a higher affinity of the wet-
ting phase for the solid surface, this phase, after displacement by
the nonwetting phase, remains as thin films on the pore walls
(Morrow, 1970; Novy et al., 1989) and as layers in the corners and
crevices. The wetting layers have nonnegligible hydraulic conduc-
tivity and can maintain phase continuity through each other as
well as small, fully wetting-phase-saturated elements. Upon fur-
ther increases in the nonwetting phase pressure (by increasing its
flow rate), the capillary pressure increases causing the fluid-fluid
interfaces (AM’s), left behind in the corners of the element by the
invading MTM, to be pushed further toward the corners. Similar to
the movement of an MTM described earlier, the AM interfaces ad-
just their curvatures to maintain their receding contact angles with
the solid surface.
Figs. 4(a)–(c) show the distributions of receding MTM and AM
contact angles determined during the drainage processes for oil-
water, gas-oil, and gas-water fluid systems, respectively. As ex-
pected, in each pair, the MTM and AM distributions exhibit similar
trends since the values of receding contact angle are independent
of the type of the fluid-fluid interface (MTM or AM) in this study.
The insignificant difference between the MTM and AM distribu-
tions, in each case, arises from the fact that measurements were
not made at the same locations. In other words, surface rough-
ness and mineralogy are not uniform through the pore space. How-
ever, we believe that if we increased the number of measurements
for both MTM and AM contact angles, it would statistically de-
crease the difference between the contact angle distributions for
each fluid system. Due to the slight difference between the distri-
butions, we combined MTM and AM contact angles and hereafter
report one receding contact angle distribution for each fluid pair
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
(a) (b)
(d) (e)
Fig. 4. Distributions of receding MTM and AM contact angles during the drainage processes of (a) Experiment A (oil-water), (b) Experiment B (gas-oil), and (c) Experiment C
(gas-water). Due to the slight difference between the distributions in each fluid system, MTM and AM contact angles were combined to generate one single receding contact
angle distribution for each fluid pair of (d) oil-water, (e) gas-oil, and (f) gas-water.
shown in Figs. 4(d)–(f). The mean receding contact angles for the
oil-water, gas-oil, and gas-water systems were 47, 37, and 35 de-
grees, respectively. It is believed that Berea sandstone is strongly
water-wet (Ma et al., 1997; Zhou et al., 20 0 0) meaning that water,
oil, and gas are the most wetting, the intermediate-wetting, and
the most nonwetting phases, respectively, in this rock. Therefore,
it is expected that the (mean) receding contact angle to be the
highest in the oil-water fluid system and the lowest in the gas-
water system. However, the difference between contact angles in
the gas-water and gas-oil fluid systems is marginal as both wa-
ter and oil are the wetting phase in the presence of gas. Contact
angle between two immiscible phases on a solid surface is deter-
mined by the Young equation and depends on fluid-fluid interfacial
and solid-fluid surface energies. Among these energy terms, solid-
gas surface energies are identical but fluid-fluid values are differ-
ent for the gas-water and the gas-oil systems. If we assume that
the contact angles are similar for both cases, there are still two
parameters (i.e., solid-water and solid-oil surface energies for the
gas-water and gas-oil systems, respectively) that can vary in order
to satisfy the Young equation for both systems.
During imbibition where the pressure of the wetting phase in-
creases (capillary pressure decreases), the direction of the move-
ment of AM interfaces is reversed. This may also happen for MTM
interfaces. For an MTM present at the entrance of an element, if
there is contact angle hysteresis, reduction in capillary pressure
causes the MTM contact angle to increase from its receding value
toward the advancing value. While the MTM contact angle hinges,
the AM angles in the corners of the element, if any, also hinge in
compliance with the local capillary pressure. When the MTM con-
tact angle reaches its advancing value, the interface invades the el-
ement and meets the AM interface(s) with a zero contact angle. As
mentioned earlier, advancing contact angles in a porous medium
287
(c)
(f)
may cover a range of values (a distribution) due to surface rough-
ness and/or mineralogical heterogeneities. Thus, an AM in an ele-
ment may reach its advancing angle sooner and move toward the
center of the element before the present MTM at the entrance of
the element does.
In the imbibition steps of each experiment (i.e., Experiments A,
B, and C), we measured both hinging and advancing contact angles
at all three saturation points. For the sake of simplicity during the
measurements, we only determined hinging contact angles from
AM interfaces and advancing contact angles from MTM interfaces.
Hinging MTM and advancing AM contact angle distributions were
considered to be similar to the obtained hinging AM and advanc-
ing MTM contact angle distributions, respectively. Hinging contact
angles were measured before AM interfaces started moving; thus,
there might be some values among the measured hinging angles
that were very close to the corresponding advancing angles. For
advancing contact angles, we tried to measure the angle when the
MTM interface had passed the entrance of the pore elements, that
is, the pore had been invaded by the wetting phase. This almost
guaranteed that the measured MTM contact angles represented ad-
vancing values.
Fig. 5 exhibits the three hinging (AM) contact angle distribu-
tions measured at the three saturation points of the imbibition
step for Experiments A, B, and C. As observed, in each fluid system,
the mean values of the distributions shifted from left (smaller an-
gles) to right (higher angles). This is because, at the beginning of
the imbibition process, the contact angles have just started hing-
ing so their values are low (closer to their receding values). How-
ever, when the imbibition process proceeds by further increases
in the wetting phase pressure, the angles hinge more until they
reach their advancing values. The minimum and maximum hing-
ing AM contact angles are listed in Table 5. As seen for each fluid
288 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
(a)
(b)
(c)
Fig. 5. Distributions of hinging AM contact angles measured at the three saturation
points during the imbibition process of (a) Experiment A (oil-water), (b) Experiment
B (gas-oil), and (c) Experiment C (gas-water).
system, the minimum and the maximum values of the three dis-
tributions are similar and do not show any specific trends. This is
also observed in Fig. 5 as the minimum and maximum values of
the three distributions are located almost at the same values, but
the mean values gradually shifted toward right when moving from
the first saturation point to the second and then the third ones. As
expected, the hinging contact angle distributions in the gas-oil and
(a)
(b)
(c)
Fig. 6. Advancing and receding contact angle distributions of (a) Experiment A (oil-
water), (b) Experiment B (gas-oil), and (c) Experiment C (gas-water). In each case,
the difference between the two distributions demonstrates contact angle hysteresis.
gas-water systems demonstrate almost the same trend (in regard
to their minimum, mean, and maximum values) as both water and
oil are the wetting phases compared to gas. These values, i.e., min-
imum, mean, and maximum, however, are larger in the water-oil
system as oil is less nonwetting than gas with respect to water.
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 289

Table 5
Statistics of receding, hinging, and advancing contact angle values for the binary-equilibrated, two-phase ex-
periments (Experiments A, B, and C).

θrMT M & θrAM θhAM θhAM θhAM θaMT M

(1st SPa ) (2nd SP) (3rd SP) (all SP’s)

Oil-Water Minimum 37 38 39 39 44
Maximum 56 63 67 65 71
Mean 47 51 53 54 57
Standard deviation 5 6 6 6 5
Number of measurements 40 20 20 20 60
Gas-Oil Minimum 28 32 35 37 35
Maximum 48 53 54 55 58
Mean 37 41 44 46 47
Standard deviation 5 5 5 5 5
Number of measurements 40 20 20 20 60
Gas-Water Minimum 28 33 31 33 37
Maximum 44 50 54 57 56
Mean 35 42 43 45 46
Standard deviation 4 5 5 6 4
Number of measurements 40 20 20 20 60
a
Saturation point in the imbibition process where contact angle measurements were made.

Table 6
Statistics of receding, hinging, and advancing contact angle values for the ternary-equilibrated, two-phase
experiments (Experiments D, E, and F).

θrMT M & θrAM θhAM θhAM θhAM θaMT M

(1st SPa ) (2nd SP) (3rd SP) (all SP’s)

Oil-Water Minimum 38 41 35 40 45
Maximum 57 65 66 66 69
Mean 46 51 54 54 58
Standard deviation 5 7 8 6 5
Number of measurements 40 20 20 20 60
Gas-Oil Minimum 27 31 35 37 35
Maximum 50 53 57 56 62
Mean 37 42 45 45 47
Standard deviation 5 5 6 6 5
Number of measurements 40 20 20 20 60
Gas-Water Minimum 22 31 30 33 35
Maximum 45 55 54 56 59
Mean 34 42 43 45 46
Standard deviation 6 6 6 6 6
Number of measurements 40 20 20 20 60
a
Saturation point in the imbibition process where contact angle measurements were made.

Measurement of advancing MTM contact angles was made for
all three saturation points as well during the imbibition process of
each experiment. Because advancing contact angles are indepen-
dent of saturation points at which measurements were made, we
combined all advancing values and generated one distribution for
each fluid pair. The advancing contact angle distributions of Exper-
iments A, B, and C are plotted in Fig. 6 along with the correspond-
ing receding contact angle distributions. In each case, the differ-
ence between the two distributions demonstrates the contact angle
hysteresis. Larger hysteresis may be observed in rock-fluid systems
with higher surface roughness, more mineralogical heterogeneities,
or greater wettability alteration. As seen in Table 5, the hystere-
sis values (the difference between the mean advancing and the
mean receding contact angles) are nearly identical (around 10 de-
grees), regardless of the fluid system. The results relatively agreed
with the values reported in the literature. For instance, advanc-
ing oil-water contact angles measured on quartz surfaces using
conventional techniques were about 32 to 43 degrees (McCaffery,
1972), whereas our results showed advancing values ranging from
44 to 71 degrees with an average of 57 degrees. The differences
between the ex- and in-situ measurements may be attributed to
the fact that in-situ measurements consider mineral heterogene-
ity and surface roughness, while the ex-situ ones overlook these
factors.
4.2.2. Ternary-equilibrated experiments
To investigate the effect of equilibration of all three phases on
two-phase flow, Experiments D (oil-water), E (gas-oil), and F (gas-
water) were performed. An identical procedure as used for Ex-
periments A, B, and C was followed with this difference that the
desired phases in each fluid pair had been brought into equilib-
rium with the third phase prior to the experiment. Fig. 7 and
Table 6 provide the results. Fig. 7 shows the distributions of ad-
vancing (MTM) and receding (MTM and AM combined) contact an-
gles for the two-phase experiments under the binary-equilibrated
(Experiments A, B, and C) and ternary-equilibrated (Experiments
D, E, and F) conditions. As observed, the distributions of con-
tact angles for the binary-equilibrated and ternary-equilibrated
tests are similar in each case. Comparison of the values listed in
Table 6 with those in Table 5 also reveals that the mean contact
angles (including receding, hinging, and advancing) have not sig-
nificantly changed in any of the three fluid systems. This finding
may be attributed to the fact that the oil phase, as showed earlier
in this study, was nonspreading. As mentioned in Section 2.1, the
equilibrium spreading coefficient for the water-oil-nitrogen system
used in this study was negative meaning that the oil phase would
form lenses on the water surface in the presence of nitrogen. How-
ever, some oil layers were visible in the pore space. The stabil-
ity of these layers, which collapse after reaching disjoining pres-
290 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298

Receding-Binary-eq. Receding-Binary-eq. Receding-Binary-eq.

Receding-Ternary-eq. Receding-Ternary-eq. Receding-Ternary-eq.
Average receding-Binary-eq. Average receding-Binary-eq. Average receding-Binary-eq.
Average receding-Ternary-eq. Average receding-Ternary-eq. Average receding-Ternary-eq.

(a) (b) (c)

Advancing-Binary-eq. Advancing-Binary-eq. Advancing-Binary-eq.

Advancing-Ternary-eq. Advancing-Ternary-eq. Advancing-Ternary-eq.
Average advancing-Binary-eq. Average advancing-Binary-eq. Average advancing-Binary-eq.
Average advancing-Ternary-eq. Average advancing-Ternary-eq. Average advancing-Ternary-eq.

(d) (e) (f)

Fig. 7. Advancing (MTM) and receding (MTM and AM combined) contact angle distributions of the two-phase experiments under the ternary- and binary-equilibrated
conditions for: (a) and (d) oil-water (Experiments A and D), (b) and (e) gas-oil (Experiments B and E), and (c) and (f) gas-water (Experiments C and F).

sure, is controlled by interfacial tension, pore geometry, wettabil-
ity, and one of the other two capillary pressures (Keller et al.,
1997; Piri and Blunt, 2004). Although experimental data on the
relation between the initial (Cso i ) and equilibrium (C eq ) spreading
so
coefficients for a given system is virtually unavailable, theoretical
work (Fenwick, 1997) has shown that the difference between the
initial and equilibrium coefficients becomes smaller as the fluid
system moves from spreading to nonspreading. Generally speaking,
the more negative the initial spreading coefficient is, the less the
difference between Cso i and C eq will be.
so
The balance of forces in a porous medium is affected by rock
properties and by an interplay of physical and chemical phenom-
ena taking place at fluid-fluid and rock-fluid interfaces. These in-
teractions are usually manifested through interfacial tension and
contact angle. Since we used similar core samples from a single
homogenous block, it is plausible to assume that the effects of pore
geometry, pore-size distribution, and surface roughness are similar
in both groups of experiments. We therefore believe that interfa-
cial tensions in this nonspreading system, no matter the two fluids
were in equilibrium with the third phase or not, would practically
stay unchanged leading to similar contact angle patterns. This ar-
gument may support our observation that equilibration of all three
phases did not influence the contact angles, and the results of Ex-
periments D, E, and F were similar to those of Experiments A, B,
and C, respectively. However, these findings may not apply to more
complicated systems in which equilibration of fluids may signifi-
cantly alter interfacial tensions.
4.3. Three-phase flow
The behavior of three-phase flow in porous media is signifi-
cantly more complicated than that of two-phase flow due to in-
volvement of additional pore-scale displacement physics, such as
double and multiple displacement chains. A double displacement
mechanism is defined as a process in which the movement of in-
terface(s) between Phase i and Phase j, e.g., gas and oil, is always
associated with the movement of interface(s) between Phase j and
Phase k, e.g., oil and water (Øren and Pinczewski, 1995). The same
definition can be extended to multiple displacement chains, such
as gas-to-oil-to-gas-to-water (van Dijke and Sorbie, 2002). When,
for example, gas is injected into a medium filled with water and
oil, it can displace water and/or oil through gas-to-water and gas-
to-oil displacements. In addition to these displacements, water and
oil may displace each other in the pore space through oil-to-water
and water-to-oil displacements. Whether the latter two displace-
ment events occur with equal frequency or one is dominant over
another is an open question for a given porous medium and satu-
ration history.
In this work, we show how one can use in-situ contact angles
to shed light on pore-scale displacement subtleties. The subject
of double displacement has been frequently discussed by scien-
tists in the literature, particularly for secondary gas injection and
tertiary waterflood processes. It has been observed in micromod-
els that, during secondary gas injection, gas-to-oil-to-water is the
dominant double displacement mechanism (Øren and Pinczewski,
1995). The occurrence of such displacement process when all three
phases are mobile has not been examined at the pore scale in
natural porous media. The network modeling results obtained for
tertiary waterfloods during water-alternating-gas injection process
(van Dijke and Sorbie, 2003) have suggested a series of double and
multiple displacement chains including a large number of water-
displacing-oil-displacing-gas and water-displacing-gas-displacing-
oil events. Although a number of studies (van Dijke and Sorbie,
20 02; 20 03; Øren et al., 1992; Øren and Pinczewski, 1994; 1995;
Piri and Blunt, 2005a,b) have been conducted using micromodels
and network modeling techniques to examine double and multiple
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 291

Sg
Oil-water contact angle-SGI
Receding oil-water contact angle-
Ternary-equilibrated
Advancing oil-water contact angle-
Ternary-equilibrated
Average oil-water contact angle-SGI

Average receding oil-water contact

angle-Ternary-equilibrated
Average advancing oil-water
contact angle-Ternary equilibrated

Point A
(a)

Sw So
1
Gas-oil contact angle-SGI
Receding gas-oil contact angle-
Fig. 8. Three-phase saturation path taken in Experiment G. The core sample, ini-
Ternary-equilibrated
tially saturated with water, was subjected to partial primary oil drainage (1) fol- Average gas-oil contact angle-SGI
lowed by gas injection (2), a waterflood (3), and then an oilflood (4). All displace- Average receding gas-oil contact angle-
Ternary-equilibrated
ments were performed using the steady-state approach.

displacement chains, to date, no micro-scale experimental research

has been conducted in natural porous media focused on the nature (b)
of three-phase displacement physics. This has consequently kept
the current understanding of the displacements at a limited level.
For instance, authors have often restricted double displacements to
scenarios in which the middle fluid is hydraulically disconnected
(van Dijke and Sorbie, 2003; Fenwick, 1997). In this work, how-
ever, we showed that double displacement events could take place
even when all three phases were mobile. It was observed that,
unlike the conventional definition, the displacement events might
not occur at exactly the same time when the middle phase was
not trapped, but they did take place during the same saturation Gas-water contact angle-SGI
Receding gas-water contact angle-
change steps resulting from fluid injection. In-situ contact angle Ternary-equilibrated
Average gas-water contact angle-SGI
distributions clearly indicated that certain groups of displacements Average receding gas-water contact
could be paired up, which was a consequence of the pressure fields angle-Ternary-equilibrated

that developed. We used direct contact angle measurements in the

pore space to provide better insights into displacement events and
investigate the likelihood of the occurrence of each displacement
event. (c)
To this end, we designed and performed a series of floods un-
der three-phase flow conditions. The core initially saturated with
water was subjected to partial primary oil drainage followed by
gas injection, a waterflood, and then an oilflood. All displacements
were performed using the steady-state approach and under the
capillary-dominated flow regime. The displacement sequences re-
sulted in a three-phase saturation path shown in Fig. 8. The core
sample was scanned after each flood when no changes were ob-
served in fluid configurations. The images were then analyzed to
determine contact angle distributions for oil-water, gas-oil, and Fig. 9. Contact angle distributions for (a) oil-water, (b) gas-oil, and (c) gas-water
gas-water pairs under three-phase flow conditions. Contact angles after the secondary gas injection (SGI) stage of the three-phase flow experiment
(Experiment G).
were measured only for MTM interfaces. Gas-water contact angles
were measured where no oil layers existed between water and
gas to eliminate the potential differences caused by the layers. The
measured contact angles were not specified as receding or advanc- were present and the fluid occupancy had changed compared to
ing at first because the exact type of each displacement was not previous step. In each section, contact angle distributions as well
known a priori. as mean values, measured for each fluid pair, are compared with
The results of each flood are presented below. As in the other the corresponding receding and/or advancing contact angle dis-
parts of this study, the individual contact angle measurements tributions and the mean values of the ternary-equilibrated, two-
were made at completely random sites. We first selected random phase experiments. The results are then supported by pore-scale
sub-volumes from each segmented image and then, in each sub- images and quantified displacement statistics. The displacement
volume, attempted to find pore sites in which all three phases statistics were not determined for the secondary gas injection be-
292 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298

Fig. 10. Two-dimensional cross-sectional views of the fluid configuration before ((a) and (c)) and after ((b) and (d)) the secondary gas injection stage of the three-phase
flow experiment (resolution = 2.34 μm for (a) and (c) and 1.5 μm for (b) and (d); brine:blue, oil:red, gas:yellow, and grains:gray; image size = 0.244 mm × 0.244 mm). (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

cause the image resolution for this process (i.e., 1.5 μm) was not Table 7
Statistics of oil-water, gas-oil, and gas-water contact angle values for the three-
the same as the one used for partial oil drainage (i.e., 2.34 μm).
phase flow experiment (Experiment G).
The objective for scanning the core after partial oil drainage was
only to ensure that we had sufficient water in the system before Secondary gas Waterflood Oilflood
injection
initiating gas injection. All analyses and the results are based on
the configurations at the end of the flooding stages. Oil-Water Minimum 39 47 36
Maximum 59 65 59
Mean 48 56 47
4.3.1. Secondary gas injection Standard deviation 5 5 6
The initial two-phase saturation condition prior to gas injec- Number of measurements 20 20 20
tion was established by partially oilflooding a water-saturated core Gas-Oil Minimum 28 33 38
sample. Afterward, the gas phase was injected into the sample Maximum 52 53 61
Mean 37 44 47
while the oil/water fractional flow was kept the same as the value
Standard deviation 6 5 5
at the end of oil drainage. Number of measurements 20 20 20
Statistics and distributions of contact angle measurements for
Gas-Water Minimum 26 36 36
oil-water, gas-oil, and gas-water are given in Table 7 and Fig. 9, Maximum 47 56 53
respectively. Also shown in Fig. 9 are the results of the ternary- Mean 35 47 44
equilibrated, two-phase flow experiments. As observed in Figs. 9(b) Standard deviation 5 5 5
Number of measurements 20 20 20
and (c), the gas-oil and gas-water contact angle distributions and
average values of the three-phase experiment are similar to those
of the two-phase experiments. This is in line with our expectation
that gas, as the most non-wetting phase, displaces water and oil, as For the case of oil-water (Fig. 9(a)), the contact angle histogram
the wetting phases, through drainage processes. It was also found is similar to the receding one of the two-phase oil-water experi-
that the presence of a third phase in the pore space in this study ment, implying that the majority of displacements were drainage
did not affect the gas-oil and gas-water contact angle distributions. (i.e., oil-displacing-water). The fluctuation in Point A, close to two-
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 293

phase advancing oil-water contact angles, could be associated with

a few water-displacing-oil events during the secondary gas injec- Oil-water contact angle-Waterflood
Advancing oil-water contact angle-
tion process. Ternary-equilibrated
Average oil-water contact angle-
Direct observation of the fluid occupancy using micro-CT im- Waterflood
ages provided further evidence to support the above-mentioned Average advancing oil-water contact
angle-Ternary-equilibrated
findings. Fig. 10 displays two-dimensional cross-sectional views
of the fluid configurations at specific locations before and af-
ter secondary gas injection in the three-phase flow experiment.
Figs. 10(a) and (c) show the initial conditions after primary oil (a)
drainage where oil resided mainly in relatively large pore elements.
Fig. 10(b) indicates that the oil in the large elements was dis-
placed during the gas injection process. This is attributed to the
fact that the gas-to-oil displacements in those elements had the
lowest threshold capillary pressures. Upon invasion of gas into the
oil-filled elements, some oil layers might form between the gas
and brine phases such as the one observed in the rectangular area
in Fig. 10(b). As seen in the encircled areas in Figs. 10(a) and (b),
oil displaced to neighboring elements may displace water, i.e., oil- Gas-oil contact angle-
displacing-water. One should note that this displacement involves Waterflood
Receding gas-oil contact
well-connected oil clusters, in contrary to the perceived notion in angle-Ternary-equilibrated
Advancing gas-oil contact
the literature that gas-displacing-oil-displacing-water occurs only angle-Ternary-equilibrated
Average gas-oil contact angle-
when oil is trapped. The continuous flow of oil during the sec- Waterflood
ondary gas injection guaranteed connectivity of the majority of oil Average receding gas-oil contact
angle-Ternary-equilibrated
clusters. Additionally, water displaced by the other two phases may Average advancing gas-oil
contact angle-Ternary-
equilibrated
also move oil from smaller pore elements, i.e., water-displacing-oil,
as seen in the square in Fig. 10(a). Visual observation along the (b)
FOV revealed that oil-to-water displacements were more frequent
and favorable than water-to-oil events during the secondary gas
injection process. Proposed displacement statistics of gas injection
components of consecutive WAG processes (van Dijke and Sorbie,
2003) agree well with our results for gas injection. Micromodel
studies of both secondary gas injection and water-alternating-gas
injection (van Dijke and Sorbie, 2003; Øren and Pinczewski, 1995)
have suggested that, for water-wet media, a series of double dis-
placements, mainly gas-to-oil-to-water, takes place.
Gas-water contact angle-Waterflood
Advancing gas-water contact angle-
Ternary-equilibrated
4.3.2. Waterflood Average gas-water contact angle-
The gas injection process was followed by a waterflood through Waterflood
Average advancing gas-water contact
decreasing the oil and gas flow rates by threefold. This led to re- angle-Ternary-equilibrated

duction in the capillary number of the system. The increase in

water-to-gas and water-to-oil fractional flows increases water pres-
sure in the pore space, which in turn decreases gas-water and oil-
(c)
water capillary pressures compared to the previous step, i.e., gas
injection. As a consequence, water displaces oil and gas from pore
elements according to their oil-water and gas-water threshold cap-
illary pressures, respectively, through direct imbibition processes.
Water layers present in the corners also swell and ultimately trap
some oil and gas clusters through the snap-off displacement mech-
anism. In addition to these displacements, oil-to-gas and gas-to-oil
events are also possible under this flow process (van Dijke and Sor-
bie, 2003). More detailed description of the waterflood process has
been provided by van Dijke and Sorbie (2003) and Sohrabi et al.
(2004). We attempted to achieve a better understanding of dom- Fig. 11. Contact angle distributions for (a) oil-water, (b) gas-oil, and (c) gas-water
after the waterflood stage of the three-phase flow experiment (Experiment G).
inant displacement mechanisms during a waterflood after gas in-
jection by means of contact angle distributions and pore-scale oc-
cupancy maps.
Fig. 11 exhibits contact angle distributions for oil-water, gas- either of these fluid pairs. Histogram of the gas-oil contact angles,
oil, and gas-water interfaces after the waterflood. As observed, oil- however, showed a bimodal distribution, which fell between the
water (Fig. 11(a)) and gas-water (Fig. 11(c)) contact angle distri- receding and the advancing contact angle distributions obtained
butions were nearly identical to their respective advancing contact in the two-phase gas-oil experiment. This implies that both oil-
angle distributions with similar mean values obtained in the two- to-gas (imbibition) and gas-to-oil (drainage) displacement events
phase experiments. These observations indicated that the oil-water could take place; nonetheless, the relative frequency of oil-to-gas
and gas-water MTM interfaces were advancing in compliance with was greater as observed in Fig. 11(b). We measured the volume of
the local decrease in respective capillary pressures. The observed the defending fluids displaced during each event and listed the re-
patterns also showed that the presence of a third phase in the pore sults for the waterflood in Table 8. The values indicate that water-
space in this study did not affect the contact angle distributions of to-oil and oil-to-gas were the most dominant displacement events
294 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298

Fig. 12. Two-dimensional cross-sectional views of the fluid configuration before ((a) and (c)) and after ((b) and (d)) the waterflood stage of the three-phase flow experiment
(resolution = 1.5 μm; brine:blue, oil:red, gas:yellow, and grains:gray; image size = 0.387 mm × 0.387 mm). (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)

Table 8 which leads to low gas-water imbibition threshold capillary pres-

Statistics indirectly representing frequency of different displacement events
sures making it extremely difficult for water to invade those ele-
taking place during the waterflood and oilflood in the thee-phase flow exper-
iment (Experiment G). ments. Figs. 12(c) and (d) reveal that the oil displaced from neigh-
boring elements may invade gas-filled elements, move gas-oil in-
Waterflood Oilflood
terfaces toward the center of the elements, and in some cases
Displacement Percentage of the Displacement Percentage of the trap the gas through snap-off (i.e., oil-displacing-gas). A three-
event pore volume event pore volume dimensional visualization of a trapped gas cluster surrounded by
water-to-gas 1.43 oil-to-gas 1.08
oil is presented in Fig. S6 in Supplementary material. Gas clusters
water-to-oil 10.77 oil-to-water 6.52
gas-to-oil 1.32 gas-to-water 1.02 displaced by the other two phases can also invade large oil-filled
oil-to-gas 4.69 water-to-gas 0.70 elements (i.e., gas-displacing-oil), as shown in Fig. 12(a) and (b).

during this flow process. One should note that the displaced vol-
ume during these events may not exactly reflect the observed rel-
ative frequency of contact angles even though they are not totally
independent. The displaced volume depends on both the relative
frequency of the event and the size of the pore elements in which
the event occurs.
Fig. 12 shows two-dimensional cross-sectional views of the fluid
configuration before ((a) and (c)) and after ((b) and (d)) the wa-
terflood. The figure exhibits direct water-to-oil displacements tak-
ing place widely in medium-sized pore elements, whereas direct
water-to-gas displacements occurred only in the form of slight in-
terface movements (rectangular areas). This could be explained by
higher interfacial tension of gas-water compared to oil-water as
well as tendency of the gas phase to reside in large elements,
4.3.3. Oilflood
As mentioned earlier, the waterflood step of the three-phase ex-
periment was followed by an oilflood. To this end, oil/water and
oil/gas fractional flows (i.e., oil/water and oil/gas flow ratios) were
increased by threefold. Based on the capillary pressure concept, it
is expected that the oil starts invading medium-sized water-filled
elements. Gas-oil interfaces may also move due to the decrease in
the gas-oil capillary pressure.
Statistical analysis and distributions of contact angles are given
in Table 7 and Fig. 13, respectively. They reveal that oil-water
(Fig. 13(a)) and gas-oil (Fig. 13(b)) contact angle distributions fol-
low the same patterns as those of the receding and advancing
distributions obtained in the two-phase experiments (Table 6 and
Figs. 7(a) and (b)). This means that the processes were drainage
and imbibition, respectively. The gas-water contact angle distribu-
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298 295

Table 9
Oil-water contact angle-Oilflood Comparison between the predicted (using the Bartell–Osterhoff constraint) and in-
Receding oil-water contact angle-
situ measured contact angles during secondary gas injection, waterflood, and oil-
Ternary-equilibrated
Average oil-water contact angle- flood.
Oilflood
Average receding oil-water contact Oil-water angle Gas-oil angle Gas-water angle
angle-Ternary-equilibrated
(secondary gas injection) (waterflood) (oilflood)

Measured Predicted Measured Predicted Measured Predicted

48 42 44 40 44 43

(a)

Analysis of the displacement events by examining two-

dimensional cross-sectional views of the fluid configurations be-
fore and after the oilflood supported our argument regarding oil-
to-water and oil-to-gas displacements (circles and triangles, re-
spectively, in Figs. 14(a) and (b)). However, the number of oil-
displacing-gas events were not significant as gas was already partly
trapped in the previous waterflood step. Very few water-to-gas and
gas-to-water displacements were also observed in the micro-CT
images, but they did not result in major interface movements in
Gas-oil contact angle-Oilflood
Advancing gas-oil contact angle- pore elements (squared areas in Figs. 14(c) and (d)). Gas either was
Ternary-equilibrated
Average gas-oil contact angle-
trapped and/or resided in large elements after the waterflood and
Oilflood could hardly be displaced by water. These observations are sup-
Average advancing gas-oil contact
angle-Ternary-equilibrated ported by the statistics in Table 8 as well.
The interfacial movements can be explained by the balance
of the rock-fluid and fluid-fluid interfacial forces in the pore
space, which provides constraints for the shape of fluid interfaces
and contact angles during each displacement event (Blunt, 2001).
(b)
The force balance can be further investigated using the Bartell–
Osterhoff constraint, as presented in the next section.

4.3.4. Bartell–Osterhoff constraint

Gas-water contact angle-
Oilflood
Receding gas-water contact
angle-Ternary-equilibrated
Advancing gas-water contact
angle-Ternary-equilibrated
Average gas-water contact
angle-Oilflood
Average receding gas-water
contact angle-Ternary-
equilibrated
Average advancing gas-water
contact angle-Ternary-
(c) equilibrated
Fig. 13. Contact angle distributions for (a) oil-water, (b) gas-oil, and (c) gas-water
after the oilflood stage of the three-phase flow experiment (Experiment G).
tion (Fig. 13(c)) was similar to the respective two-phase advanc-
ing contact angle distribution with a slight shift toward the two-
phase, gas-water receding distribution. We believe that this shift
might have happened due to gas-water interface adjustment. In
other words, although the gas/water fractional flow was kept con-
stant, gas-water capillary pressure in some pore elements where
gas was trapped increased, and therefore gas-water contact angles
in those elements slightly hinged toward receding values.
The horizontal force balance of rock-fluid and fluid-fluid inter-
facial tensions for a given pair of fluids residing on a solid sur-
face is determined by the Young equation. In the context of three-
phase flow, the Young equation can be written for three two-
phase systems, i.e., oil-water-solid, gas-oil-solid, and gas-water-
solid, and then the resulting equations can be manipulated and
simplified to derive the following constraint, known as the Bartell–
Osterhoff equation, that relates contact angles and interfacial ten-
sions (Bartell and Osterhoff, 1927; Blunt, 2001; Johnson and Dettre,
1993; Zhou and Blunt, 1997):
γgw
eq
cos θgw = γgo
eq
cos θgo + γow
eq
cos θow (2)
where θ gw , θ go , and θ ow denote gas-water, gas-oil, and oil-water
contact angles, respectively. This equation implies that, in a three-
phase system under thermodynamic equilibrium with known in-
terfacial tensions, only two of the contact angles need to be known
and the third one can be calculated. The Bartell–Osterhoff con-
straint has been used to estimate dependent contact angles (ad-
vancing or receding) in pore-network modeling (Piri and Blunt,
2005a) and to explain the possible wetting orders in three-phase
flow (Sorbie and van Dijke, 2004).
We used the Bartell–Osterhoff equation to estimate oil-water,
gas-oil, and gas-water contact angles during the secondary gas in-
jection, waterflood, and oilflood processes, respectively, and then
compared the estimated values with the measured counterparts
obtained from the pore-scale images of the present study (Table 9).
The input IFT and contact angle values for Eq. (2) in each case
were obtained from Tables 2 and 7, respectively. The results given
in Table 9 show good agreements between the measured and cal-
culated values with some negligible differences, which can be at-
tributed to heterogeneity of the pore space as well as using average
contact angles instead of pore-by-pore investigation of the Bartell–
Osterhoff equation. Based on the above-mentioned agreement, we
believe if one measures pore-scale contact angles in a given ho-
mogeneous pore element, the values will be consistent with the
296 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298

Fig. 14. Two-dimensional cross-sectional views of the fluid configuration before ((a) and (c)) and after ((b) and (d)) the oilflood stage of the three-phase flow experiment
(resolution = 1.5 μm; brine:blue, oil:red, gas:yellow, and grains:gray; image size = 0.372 mm × 0.372 mm). (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)

values predicted by the Bartell–Osterhoff equation in that specific displacement mechanisms during each flow stage. Based on the
element. analysis of the experimental data, the following remarks are made:

5. Summary and final remarks
In the present study, we used a custom-built miniature core-
flooding setup integrated with a high-resolution micro-CT scanner
to map fluid configurations in the pore space of Berea sandstone
and to determine in-situ Arc Meniscus (AM) and Main Terminal
Meniscus (MTM) contact angles directly from micro-CT images. The
contact angle measurements were employed to characterize wet-
tability of the rock. We performed six sets of two-phase and one
set of three-phase flow experiments on miniature core samples us-
ing a brine/oil/nitrogen fluid system. We purposely selected an oil
phase that was nonspreading in the presence of brine and nitro-
gen. For the two-phase flow experiments, each pair of fluids (i.e.,
oil-water, gas-oil, and gas-water) was used to conduct two cycles
of drainage-imbibition experiments; one cycle when only the two
respective fluids were equilibrated prior to use (binary-equilibrated
test) and the other cycle when all three fluids were equilibrated
before using the two desired fluids (ternary-equilibrated test). For
the three-phase experiment set, the water-saturated core sample
was subjected to partial oil drainage followed by gas injection, a
waterflood, and then an oilflood. In this experiment, the contact
angle distributions and pore-scale observations were used to study
• For the binary-equilibrated two-phase experiments, the distri-
butions of receding AM and MTM contact angles exhibited sim-
ilar trends for each fluid pair. The mean receding contact angles
for the oil-water, gas-oil, and gas-water systems were 47, 37,
and 35 degrees, respectively.
• The average hinging contact angles measured during the imbi-
bition steps of the binary-equilibrated two-phase experiments
increased due to increases in the wetting-phase pressure.
• Average advancing oil-water, gas-oil, and gas-water contact an-
gles for the binary-equilibrated two-phase experiments were
57, 47, and 46 degrees, respectively. Differences between the re-
ceding and advancing distributions demonstrated contact angle
hysteresis of approximately 10 degrees.
• The results of the binary- and ternary-equilibrated two-phase
experiments were similar for each fluid pair. This indicates that,
for a nonspreading system with low mutual phase solubility,
equilibration with the third phase in the fluid system does not
impact the wetting characteristics of each fluid pair.
• During gas injection in the three-phase experiment set, the
oil-water contact angle histogram was similar to the reced-
ing one of the two-phase oil-water experiment, implying that
the majority of displacements involving oil and water were
 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
oil-displacing-water; however, a few water-displacing-oil events
were also observed.
• The observed pattern of gas-oil contact angles during the wa-
terflood showed a bimodal distribution, which fell between the
receding and the advancing contact angle distributions obtained
in the two-phase gas-oil experiment. This revealed that both
oil-to-gas and gas-to-oil displacement events could take place.
However, the relative frequency of the former was greater.
• For the oilflood process of the three-phase experiment set, it
was found that the gas-water contact angle distribution was
similar to the two-phase, gas-water advancing contact angle
distribution with a slight shift toward the two-phase, gas-
water receding distribution. It was believed that, although the
gas/water fractional flow was kept constant during the oilflood
process, gas-water capillary pressure in some pore elements
where gas was trapped increased, and therefore gas-water con-
tact angles in those elements slightly hinged toward receding
values.
• Fluid occupancy maps generated using micro-CT images pro-
vided further evidences to support the above-mentioned find-
ings.
• Calculated contact angles using the Bartell–Osterhoff equation
agreed well with the measurements with some negligible dif-
ferences, which were attributed to the heterogeneity of the
pore space as well as the use of average contact angles in-
stead of pore-by-pore investigation of the Bartell–Osterhoff
constraint.
Acknowledgment
We gratefully acknowledge financial support of Hess Corpo-
ration and the School of Energy Resources at the University of
Wyoming.
Supplementary material
Supplementary material associated with this article can be
found, in the online version, at 10.1016/j.advwatres.2016.10.009
References
Adamson, A.W., 1990. Physical Chemistry of Surfaces, 5th ed. John Wiley, New York.,
p. 777pp.
Al-Gharbi, M.S., Blunt, M.J., 2005. Dynamic network modeling of two-phase drainage
in porous media. Phys. Rev. E 71, 016308. http://dx.doi.org/10.1103/PhysRevE.71.
016308.
Alizadeh, A.H., Ioannidis, M.A., Piri, M., 2011. CO2 -saturated brine flooding: an ef-
fective process for mobilization and recovery of waterflood residual oil. Paper
SCA2011-07 Presented at the International Symposium of the Society of the
Core Analysts, Austin, Texas, US, 18–21 September.
Alizadeh, A.H., Khishvand, M., Ioannidis, M.A., Piri, M., 2014. Multi-scale experimen-
tal study of carbonated water injection: an effective process for mobilization
and recovery of trapped oil. Fuel 132, 219–235. http://dx.doi.org/10.1016/j.fuel.
2014.04.080.
Alizadeh, A.H., Piri, M., 2014a. The effect of saturation history on three-phase rela-
tive permeability: an experimental study. Water Resour. Res. 50 (2), 1636–1664.
http://dx.doi.org/10.1002/2013WR014914.
Alizadeh, A.H., Piri, M., 2014b. Three-phase flow in porous media: a review of
experimental studies on relative permeability. Rev. Geophys. 52 (3), 468–521.
http://dx.doi.org/10.10 02/2013RG0 0 0433.
Anderson, W.G., 1986a. Wettability literature survey – part 1: rock/oil/brine inter-
actions and the effects of core handling on wettability. J. Pet. Technol. 38 (10),
1125–1144. http://dx.doi.org/10.2118/13932-PA.
Anderson, W.G., 1986b. Wettability literature survey – part 2: wettability measure-
ment. J. Pet. Technol. 38 (11), 1246–1262. http://dx.doi.org/10.2118/13933-PA.
Andrew, M., Bijeljic, B., Blunt, M.J., 2014. Pore-scale contact angle measurements
at reservoir conditions using X-ray microtomography. Water Resour. 68, 24–31.
http://dx.doi.org/10.1016/j.advwatres.2014.02.014.
Armstrong, R.T., Porter, M.L., Wildenschild, D., 2012. Linking pore-scale interfacial
curvature to column-scale capillary pressure. Adv. Water Resour. 46, 55–62.
http://dx.doi.org/10.1016/j.advwatres.2012.05.009.
Arns, C.H., Bauget, F., Limaye, A., Sakellariou, A., Senden, T.J., Sheppard, A.P.,
Sok, R.M., Pinczewski, W.V., Bakke, S., Berge, L.I., Øren, P.E., Knackstedt, M.A.,
2005. Pore-scale characterization of carbonates using X-ray microtomography.
SPE J. 10 (4), 475–484. http://dx.doi.org/10.2118/90368-PA.
297
Bartell, F.E., Merrill, E.J., 1932. Determination of adhesion tension of liquids against
solids: a microscopic method for the measurement of interfacial contact angles.
J. Phys. Chem. 36 (4), 1178–1190.
Bartell, F.E., Osterhoff, H.J., 1927. Determination of the wettability of a solid by a
liquid. Ind. Eng. Chem. 19 (11), 1277–1280.
Blunt, M.J., 2001. Constraints on contact angles for multiple phases in thermody-
namic equilibrium. J. Colloid Interface Sci. 239 (1), 281–282. http://dx.doi.org/
10.10 06/jcis.20 01.7534.
Buckley, J.S., 2001. Effective wettability of minerals exposed to crude oil. Curr. Opin.
Colloid Interface Sci. 6 (3), 191–196. http://dx.doi.org/10.1016/S1359-0294(01)
0 0 083-8.
Cuiec, L., 1984. Rock/crude-oil interactions and wettability: an attempt to under-
stand their interrelation. In: Paper SPE 13211, proceedings of the SPE Annual
Technical Conference and Exhibition, Houston, Texas, 16–19 September.
van Dijke, M.I.J., Sorbie, K.S., 2002. Pore-scale network model for three-phase flow
in mixed-wet porous media. Phys. Rev. E 66 (4). http://dx.doi.org/10.1103/
PhysRevE.66.046302.
van Dijke, M.I.J., Sorbie, K.S., 2003. Pore-scale modelling of three-phase flow in
mixed-wet porous media: multiple displacement chains. J. Pet. Sci. Eng. 39 (3–
4), 201–216. http://dx.doi.org/10.1016/S0920-4105(03)0 0 063-9.
Fenwick, D.H., 1997. Pore scale modeling of three-phase flow. Stanford University,
Stanford, California PhD dissertation.
Hassanizadeh, S.M., Gray, W.G., 1993. Thermodynamic basis of capillary pressure in
porous media. Water Resour. Res. 29 (10), 3389–3405. http://dx.doi.org/10.1029/
93WR01495.
Hirasaki, G.J., 1991. Wettability: fundamentals and surface forces. SPE Form. Eval. 6
(2), 217–226. http://dx.doi.org/10.2118/17367-PA.
Iglauer, S., Favretto, S., Spinelli, G., Schena, G., Blunt, M.J., 2010. X-ray tomography
measurements of power-law cluster size distributions for the nonwetting phase
in sandstones. Phys. Rev. E 82, 056315. http://dx.doi.org/10.1103/PhysRevE.82.
056315.
Israelachvili, J.N., 2011. Intermolecular and Surface Forces, third ed. Academic Press,
Boston.
Johnson, R., Dettre, R., 1993. Wetting of Low-energy Surfaces, 49. Marcel Dekker,
New York.
Karpyn, Z.T., Grader, A.S., Halleck, P.M., 2007. Visualization of fluid occupancy in a
rough fracture using micro-tomography. J. Colloid Interface Sci. 307 (1), 181–
187. http://dx.doi.org/10.1016/j.jcis.2006.10.082.
Keller, A.A., Blunt, M.J., Roberts, P.V., 1997. Micromodel observation of the role of oil
layers in three-phase flow. Transp. Porous Media 26 (3), 277–297.
Khishvand, M., Akbarabadi, M., Piri, M., 2016. Micro-scale experimental investigation
of the effect of flow rate on trapping in sandstone and carbonate rock samples.
Adv. Water. Resour. 94, 379–399. http://dx.doi.org/10.1016/j.advwatres.2016.05.
012.
Ma, S., Morrow, N.R., Zhang, X., 1997. Generalized scaling of spontaneous imbibition
data for strongly water-wet systems. J. Pet. Sci. Eng. 18 (34), 165–178. http://dx.
doi.org/10.1016/S0920-4105(97)0 0 020-X.
Mason, G., Morrow, N.R., 1987. Meniscus configurations and curvatures in non-ax-
isymmetric pores of open and closed uniform cross section. Proc. R. Soc. Lond.
A Math. Phys. Sci. 414 (1846), 111–133.
Mason, G., Morrow, N.R., 1991. Capillary behavior of a perfectly wetting liquid in
irregular triangular tubes. J. Colloid Interface Sci. 141 (1), 262–274. http://dx.
doi.org/10.1016/0021-9797(91)90321-X.
Mason, G., Morrow, N.R., Walsh, T., 1988. Capillary properties of pores formed by
two unequal parallel rods and a plate. In: Unger, K.K., Rouquerol, J., Sing, K.S.W.,
Kral, H. (Eds.), Characterization of Porous Solids Proceedings of the IUPAC Sym-
posium (COPS I), Bad Soden a. Ts.. In: Studies in Surface Science and Catalysis,
39. Elsevier, pp. 243–252. http://dx.doi.org/10.1016/S0167- 2991(09)60748- 5.
McCaffery, F.G., 1972. Measurement of interfacial tensions and contact angles at
high temperature and pressure. Phys. Rev. E 11, 26–32. http://dx.doi.org/10.2118/
72- 03- 03.
Morrow, N.R., 1970. Irreducible wetting-phase saturations in porous media. Chem.
Eng. Sci. 25, 1799–1815. http://dx.doi.org/10.1016/0 0 09-2509(70)80 070-7.
Morrow, N.R., 1975. The effects of surface roughness on contact: angle with special
reference to petroleum recovery. J. Can. Pet. Technol. 14 (4), 42–53. http://dx.
doi.org/10.2118/75- 04- 04.
Morrow, N.R., 1990. Wettability and its effect on oil recovery. J. Pet. Technol. 42 (12),
1476–1484. http://dx.doi.org/10.2118/21621-PA.
Morrow, N.R., Nguyen, M.D., 1982. Effect of interface velocity on dynamic contact
angles at rough surfaces. J. Colloid Interface Sci. 89 (2), 523–531. http://dx.doi.
org/10.1016/0021-9797(82)90203-X.
Novy, R., Toledo, P., Davis, H., Scriven, L., 1989. Capillary dispersion in porous media
at low wetting phase saturations. Chem. Eng. Sci. 44, 1785–1797. http://dx.doi.
org/10.1016/0 0 09- 2509(89)85121- 8.
Oliver, J.P., Huh, C., Mason, S.G., 1980. An experimental study of some effects of solid
surface roughness on wetting. Colloids Surfaces 1 (1), 79–104. http://dx.doi.org/
10.1016/0166-6622(80)80039-4.
Øren, P.E., Billiotte, J., Pinczewski, W.V., 1992. Mobilization of waterflood residual oil
by gas injection for water-wet conditions. SPE Form. Eval. 7 (1), 70–78. http://
dx.doi.org/10.2118/20185-PA.
Øren, P.E., Pinczewski, W.V., 1994. The effect of wettability and spreading coeffi-
cients on the recovery of waterflood residual oil by miscible gasflooding. SPE
Form. Eval. 9 (2), 149–156. http://dx.doi.org/10.2118/24881-PA.
Øren, P.E., Pinczewski, W.V., 1995. Fluid distribution and pore-scale displacement
mechanisms in drainage dominated three-phase flow. Transp. Porous Media 20
(1–2), 105–133. http://dx.doi.org/10.10 07/BF0 0616927.
298 M. Khishvand et al. / Advances in Water Resources 97 (2016) 279–298
Piri, M., Blunt, M.J., 2004. Three-phase threshold capillary pressures in noncircular
capillary tubes with different wettabilities including contact angle hysteresis.
Phys. Rev. 70 (2). http://dx.doi.org/10.1103/PhysRevE.70.061603.
Piri, M., Blunt, M.J., 2005a. Three-dimensional mixed-wet random pore-scale net-
work modeling of two- and three-phase flow in porous media. I. Model de-
scription. Phys. Rev. E 71, 026301. http://dx.doi.org/10.1103/PhysRevE.71.026301.
Piri, M., Blunt, M.J., 2005b. Three-dimensional mixed-wet random pore-scale net-
work modeling of two- and three-phase flow in porous media. II. Results. Phys.
Rev. E 71, 026302. http://dx.doi.org/10.1103/PhysRevE.71.026302.
Sanei, S.H.R., Fertig, R.S., 2015. Uncorrelated volume element for stochastic modeling
of microstructures based on local fiber volume fraction variation. Compos. Sci.
Technol. 117, 191–198. http://dx.doi.org/10.1016/j.compscitech.2015.06.010.
Saraji, S., Goual, L., Piri, M., Plancher, H., 2013. Wettability of supercritical carbon
dioxide/water/quartz systems: simultaneous measurement of contact angle and
interfacial tension at reservoir conditions. Langmuir 29 (23), 6856–6866.
Sohrabi, M., Tehrani, D.H., Danesh, A., Henderson, G.D., 2004. Visualization of oil re-
covery by water-alternating-gas injection using high-pressure micromodels. SPE
J. 9 (3), 290–301. http://dx.doi.org/10.2118/890 0 0-PA.
Sorbie, K.S., van Dijke, M.I.J., 2004. Fundamentals of Three-phase Flow in Porous
Media of Heterogeneous Wettability. Institute of Petroleum Engineering, Heri-
ot-Watt University, Edinburgh, Scotland.
Treiber, L.E., Archer, D.L., Owens, W.W., 1972. A laboratory evaluation of the wetta-
bility of fifty oil-producing reservoirs. SPE J. 12 (6), 531–540. http://dx.doi.org/
10.2118/3526-PA.
Wildenschild, D., Sheppard, A.P., 2013. X-Ray imaging and analysis techniques for
quantifying pore-scale structure and processes in subsurface porous medium
systems. Adv. Water Resour. 51, 217–246. 35th Year Anniversary Issue. http://dx.
doi.org/10.1016/j.advwatres.2012.07.018
Zhou, D., Blunt, M.J., 1997. Effect of spreading coefficient on the distribution of light
non-aqueous phase liquid in the subsurface. J. Contam. Hydrol. 25, 1–19.
Zhou, D., Blunt, M.J., 1998. Wettability effects in three-phase gravity drainage. J. Pet.
Sci. Eng. 20 (34), 203–211. http://dx.doi.org/10.1016/S0920-4105(98)0 0 021-7.
Zhou, X., Morrow, N.R., Ma, S., 20 0 0. Interrelationship of wettability, initial water
saturation, aging time, and oil recovery by spontaneous imbibition and water-
flooding. SPE J. 5 (2), 199–207. http://dx.doi.org/10.2118/62507-PA.