Article

pubs.acs.org/Langmuir

Correlation of Oil−Water and Air−Water Contact Angles of Diverse

Silanized Surfaces and Relationship to Fluid Interfacial Tensions
Jay W. Grate,* Karl J. Dehoff, Marvin G. Warner, Jonathan W. Pittman, Thomas W. Wietsma,
Changyong Zhang, and Mart Oostrom
Pacific Northwest National Laboratory, PO Box 999, Richland, Washington 99352, United States

ABSTRACT: The use of air−water, θwa, or air−liquid contact angles is

customary in surface science, while oil−water contact angles, θow, are of
paramount importance in subsurface multiphase flow phenomena including
petroleum recovery, nonaqueous phase liquid fate and transport, and
geological carbon sequestration. In this paper we determine both the air−
water and oil−water contact angles of silica surfaces modified with a diverse
selection of silanes, using hexadecane as the oil. The silanes included
alkylsilanes, alkylarylsilanes, and silanes with alkyl or aryl groups that are
functionalized with heteroatoms such as N, O, and S. These silanes yielded
surfaces with wettabilities from water wet to oil wet, including specific silanized surfaces functionalized with heteroatoms that
yield intermediate wet surfaces. The oil−water contact angles for clean and silanized surfaces, excluding one partially fluorinated
surface, correlate linearly with air−water contact angles with a slope of 1.41 (R = 0.981, n = 13). These data were used to examine
a previously untested theoretical treatment relating air−water and oil−water contact angles in terms of fluid interfacial energies.
Plotting the cosines of these contact angles against one another, we obtain the relationship cos θwa = 0.667 cos θow + 0.384
(R = 0.981, n = 13), intercepting cos θow = −1 at −0.284, which is in excellent agreement with the linear assumption of the
theory. The theoretical slope, based on the fluid interfacial tensions σwa, σow, and σoa, is 0.67. We also demonstrate how silanes
can be used to alter the wettability of the interior of a pore network micromodel device constructed in silicon/silica with a glass
cover plate. Such micromodels are used to study multiphase flow phenomena. The contact angle of the resulting interior was
determined in situ. An intermediate wet micromodel gave a contact angle in excellent agreement with that obtained on an open
planar silica surface using the same silane.

1. INTRODUCTION
Wettability is an important property of surfaces involved in
multiphase processes.1,2 Given accessible surfaces of suitable
geometry, this property can be probed by measuring the
contact angle, θ, which is, in turn, related to interfacial tensions.
The contact angles for two-fluid air−water and oil−water systems
are related to interfacial tensions according to the Young
equation,3 conventionally in current literature as follows:
σsa = σsw + σwa cos θwa (1a)

σso = σsw + σow cos θow (1b)

where σ are the interfacial tensions and the subscripts a, w, o,
and s denote the air, water, oil, and the solid, respectively. For
the systems to be described below, the air−water and oil−water
contact angles, θwa and θow, respectively, are the angles through
the water phase at the junction of the water, the solid, and the
remaining fluid phase, air or oil. For a drop of water on a solid
surface in air, the contact angle is in the water droplet. For a
drop of oil on a surface in a surrounding fluid of water, the con-
tact angle is outside the oil droplet in the water. These angles
are shown in Figure 1 along with the relevant interfacial tensions.
The contact angle has been used as a means to characterize
material surfaces and to investigate functionally modified inter-
faces.4,5 Given a sufficient number of contact angle and related
measurements, surface interfacial tensions can be determined.
Figure 1. Diagrams for the air−water and oil−water contact angles (θ)
as described in the text, indicating the interfacial tensions (σ) in eq 1.
The water droplet in air rests on top of the surface. The oil droplet
contacts the surface in an inverted configuration because oil is less
dense than water. The DROP software used measures the angle in the
drop (M.A., measured angle), which coincides with the air−water
contact angle in the water drop but is the complement of the oil−
water contact angle.
The meaning and use of the contact angle in surface science
were elucidated in pioneering works by Fox, Zisman, Girifalco,
Received: November 3, 2011
Revised: January 17, 2012
Published: February 24, 2012

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Langmuir
Good, Fowkes, and others.6−14 The vast majority of research
about, or using, the contact angle in surface science has addressed
liquid−air contact angles. Most frequently, the liquid is water. Air−
water contact angles for smooth surfaces range from 0 to a limit
of 120°.15−17
While the air−water contact angle predominates in the char-
acterization of materials and functionally modified surfaces, the
oil−water contact angle is of paramount importance in charac-
terizing the wettability of porous materials involved in multi-
phase phenomena. Wettability is a critical parameter influenc-
ing immiscible fluid behaviors in porous media1,2 that are
relevant to geological carbon sequestration,18−22 nonaqueous
phase liquid (NAPL) contaminant fate and transport,23−28 and
petroleum recovery.1,29−32 Wettability influences capillary
pressures, relative permeabilities, and multiphase fluid distribu-
tions at the pore scale. The contact angle is related to the
capillary pressure, Pc. For an oil−water system in a cylindrical
capillary, the relationship is described by the following form of
the Young−Laplace equation:
2σow cos θow
Pc =
r (2)
Strong water wettingwhere the contact angle θ approaches
zero and hence cos θ approaches oneyields the highest
capillary pressures. When the contact angle approaches 90°, cos
θ approaches zero, and the two interfaces involving the solid
surface have equal interfacial tensions. Surface wettability has
been defined as water wet for oil−water contact angles from 0
to 75°, intermediate wet from 75 to 115°, and oil wet from 115
to 180°. The region from 55 to 75° is considered weakly water
wet, while contact angles from 115 to 135° are weakly oil wet.2
Despite the extensive research on wettability, contact angles,
and interfacial tensions, the relationships between the air−
water contact angle and the oil−water contact angles have not
been thoroughly examined. Few investigations determine both
the air−water and oil−water contact angles on the same sur-
faces, and even fewer correlate these data. A report by Tamai
et al. represents a counterexample in the characterization of
material surfaces. These authors measured air−water and oil−
water contact angles on three organic polymer surfaces: PMMA,
PVC, and PTFE.33 From the reported angles, we find an average
ratio of isooctane−water/air−water contact angles of 1.55 on
these solid polymers. With regard to modified surfaces, the work
of Wei et al. is notable.34 These authors measured the air−water
and oil−water contact angles (Soltrol 130 oil) for unmodified
and four silane-modified glass surfaces, comprising three
aklylsilanes and one alkylarylsilane. These authors plotted cos
θow against cos θwa, observing that the data were “remarkably
linear”. No slopes, intercepts, or comparisons with theory were
reported in this paper. From their tabulated advancing contact
angles, we find Soltrol 130−water/air−water contact angle ratios
of 1.41, 1.42, 1.44, and 1.52 for the silane-treated surfaces.
Several years after the work by Wei et al., van Dijke and
Sorbie35 published a theoretical paper on the physics and pore
occupancy of weakly wetted three phase systems and
relationships between air−water, oil−water, and air−oil contact
angles were derived. Starting with the Bartell−Osterhof
equation,36,37 given here as eq 3, van Dijke and Sorbie related
the cos θwa to the cos θow for nonspreading oils (σwa < (σoa − σow))
using known end-point conditions for strongly water wet (cos θow =
1; cos θwa = 1) and oil wet (cos θow = −1; cos θwa = (σoa − σow)/
(σwa)) pores. Note that the Bartell−Osterhof equation can be
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derived from the Young’s equations for air−water (eq 1a), oil−
water (eq 1b), and oil−air contact angles.
σwa cos θwa = σoa cos θoa + σow cos θow (3)
Van Dijke and Sorbie recognized that due to a lack of knowl-
edge on the relationships for the contact angles between the
two end points, they could only apply the minimum assump-
tion (e.g., any relation could be possible) for that region. In
their discussion, they illustrated potential relations by consider-
ing several quadratic forms, and the linear assumption as shown
in eq 4.
⎡ 1 − (σoa − σow )/σwa ⎤
cos θwa = ⎢ ⎥ cos θow
⎣ 2 ⎦
⎡ 1 + (σoa − σow )/σwa ⎤
+⎢ ⎥
⎣ 2 ⎦ (4)
For this assumption, the slope of the line correlating cos θwa on
the y-axis to the cos θow on the x-axis passes is determined from
the fluid interfacial tensions as (σoa − σow)/(σwa).35 Van Dijke
and Sorbie stated that “given the profound and far reaching
consequences of the contact angle relationships” discussed
here, it would be of vital importance to experimentally verify
the exact form of these relationships. It is therefore remarkable
that the relationships between air−water and oil−water contact
angles have never been experimentally tested for diverse surfaces.
While of considerable fundamental importance, wettability is
also of practical research importance with regard to methods
and devices for studying multiphase flow. The behaviors of
immiscible fluids can be directly observed in experimental
structures such as capillaries, Hele−Shaw cells, fracture models,
thin packed beds of particles, and etched pore network micro-
models.30,38−45 The wettabilities of the surfaces in these
structures are typically determined by the materials of con-
struction, where truly clean glass and silica surfaces are water
wet, while polymer resin and polydimethylsiloxane (PDMS)
surfaces are oil wet.46,47 Our current research is focused on the
use of pore network micromodels to investigate immiscible
fluid displacements at ambient pressures over a range of fluid
viscosities and flow rates as well as high-pressure investigations
with liquid and supercritical CO2.41−43 The pore networks are
dry-etched in silicon and oxidized to prepare a silica surface.
These structures are sealed with a transparent glass cover plate
by anodic bonding. Freshly cleaned surfaces of silica or glass are
water wet. There is a need to control the wettability of the
internal surfaces in order to perform parallel studies in other-
wise identical pore networks where surfaces are water wet,
intermediate wet, or oil wet.
While silanization is the best known covalent chemistry for
altering wettabilities of silica and glass,17,34,48,49 the majority of
efforts to alter particles or surfaces for multiphase fluid studies
to date have focused on the conversion of water wet to oil wet
using silanes with alkyl groups to render surfaces hydro-
phobic.34,50−53 However, the use of specific silanizing reagents
to obtain intermediate wet surfaces as measured by the oil−water
contact angle has not been adequately addressed. In addition,
while there are abundant data in the literature on the air−water
contact angles of surfaces modified with diverse silanes, there are
much less data on the oil−water contact angles. Hence, silanized
surfaces characterized by the air−water contact angle cannot
necessarily be used to predict the wettability in terms of the oil−
water contact angle.
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Table 1. Contact Angle Measurements on Silica and Silanized Silica Surfaces

air−water oil−waterb
std meas meas std
surface modification on silica median mean dev n median mean median mean dev n
UV-ozone cleaned 3.3 3.3 0.6 9 168 167 12 13 3.1 9
SC1 cleaned 3.4 3.7 0.8 9 169 169 11 11 3.3 9
sulfonic acid terminated silanea 15 16 5.1 9 157 155 23 25 3.8 9
aminopropyltriethoxysilane 22 24 10.6 16 151 149 29 31 5.4 12
N-(trimethoxysilylethyl)benzyl-N,N,N-trimethylammonium 28 34 15.2 14 115 113 65 67 7.5 9
chloride
N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride 50 48 13.9 17 109 107 71 73 5.5 9
mercaptopropyltriethoxysilane 69 69 1.7 10 83 83 97 97 3.1 9
2-(3-trimethoxysilylpropylthio)thiophene 76 75 1.6 9 81 80 99 100 5.2 9
triethoxy-2-thienylsilane 79 79 1.7 9 83 85 97 95 3.1 9
1,3-diphenyltetramethyldisilazane 89 88 3.0 9 44 44 136 136 2.5 9
hexamethyldisilazane 96 97 2.2 9 42 40 138 140 4.9 9
nonafluorohexyltrimethoxysilane 97 99 4.8 9 66 67 114 113 3.1 9
dodecyltriethoxysilane 103 102 1.9 9 33 32 147 148 4.7 9
isooctyltrichlorosilane 105 105 4.3 9 44 42 136 138 9.1 9
a
Aminopropyltriethoxysilane was coupled via amide bond (using EDC/NHC coupling method) to sulfoacetic acid prior to surface silanization.
b
Hexadecane is the oil.

In this article, we report data on the air−water and oil−water
contact angles obtained by modifying the silica surface on
oxidized silicon wafer materials with a wide range of silane
reagents, including alkylsilanes, alkylarylsilanes, and silanes with
alkyl or aryl groups that are functionalized with heteroatoms
such as N, O, and S. Silica surfaces are relevant to our pore
network micromodels and may be preferred for fundamental
studies because they are generally easier to prepare and modify
with silanes than glass surfaces. We have used the data on these
surfaces to test the theory of van Dijke and Sorbie by plotting
cos θwa against cos θow, thus providing an experimental verifi-
cation of this theory as a matter of fundamental science. From a
practical point of view, we have found heteroatom-containing
silanes that produce intermediate wet surfaces as determined by
oil−water contact angle measurements. The silanization rea-
gents and contact angle data presented here can facilitate the
use of experimental systems with controlled wettability and
could be used to modify natural materials (e.g., siliceous rocks)
in controlled ways.54−56 We demonstrate the modification of
the interior surfaces of a pore network micromodel with a silane
to prepare an intermediate wet surface.
2. EXPERIMENTAL SECTION
Surface Preparation and Modification with Silanes. The
silanes used for surface modifications are listed in Table 1 and were
used as purchased except the sulfoacetic acid reagent, which was syn-
thesized by EDC/NHS coupling of sulfoacetic acid to aminopropyl-
triethoxysilane (EDC and NHS refer to 1-ethyl-3-(3-(dimethylamino)-
propyl) carbodiimide and N-hydroxysuccinimide, respectively).57,58
From a 10 cm diameter silicon wafer, 3 cm by 1 cm rectangles were cut
in order to fit the contact angle instrument. Two methods were used
to clean the rectangular pieces. The first method used Standard Clean
1 (SC1) conditions.59 The surfaces were submerged in a 70 °C solu-
tion of 5 parts deionized (DI) water, 1 part 27% ammonium
hydroxide, and 1 part 30% hydrogen peroxide for 10 min, followed by
a DI water rinse. The second cleaning method used ultraviolet (UV)-
ozone.59 The surfaces were rinsed with chloroform, isopropanol, and
ethanol followed by UV-ozone treatment for 30 min in a Jelight model
342 UV-ozone cleaner. Both methods gave similar contact angles for
the bare silica surface on the silicon pieces. The UV-ozone method was
used to prepare the 3 cm by 1 cm rectangles for silanization, while the
SC1 conditions were used for preparing the interiors of silicon/silica/
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glass micromodels for silanization where the UV-ozone treatment is
not feasible. Three UV-ozone cleaned pieces were placed in a small
glass jar lined with aluminum foil and the target silane was pipetted
over the surfaces. The jar was sealed with a poly screw top lid and
placed in a 90 °C oven for 15 h. Afterward, the surfaces were washed
with water, hexanes, and methanol to remove excess silane material
and dried under a stream of nitrogen gas.
Contact Angle Determinations. Contact angle measurements
were performed with a Ramé-Hart Model 500 advanced goniometer
(Netcong, NJ) using the static sessile drop method with DROP Image
Advanced Software to determine static contact angles. Air−water
contact angles were obtained for water droplets in air and oil−water
contact angles for hexadecane droplets in water. Water was obtained
from a Thermo Scientific Barnstead Nanopure (Fisher Scientific, New
York, NY) water filtration system, and hexadecane (>99% purity) was
from Sigma-Aldrich (St. Louis, MO). For each chemical treatment
listed in Table 1, the behaviors of at least three drops of water and
hexadecane were evaluated on each of the three prepared surfaces.
Prior to taking measurements, the instrument’s stage was leveled with
a “bulls-eye” style level and then checked again with the programs
baseline leveling feature, which uses the systems camera to determine
if the surface is flat after each silicon piece is loaded. Drops were
created with a Ramé-Hart microsyringe assembly connected to a 22
gauge needle and then contacted with the surface. After a drop was
transferred to the silicon surface, observations were made to ensure
that the contact angle was stable, and then a two-dimensional image
was captured by the system software. On the image, a horizontal
baseline is set along the interface between the drop and the sample’s
surface, which is used as a reference line to measure the contact angle.
The software also measures the drop’s height, width, profile area, and
approximate volume and subsequently computes the contact angle by
fitting a curve to a circular profile. Drop volumes were typically in the
range of 3−7 μL. Static contact angles measured as described were
taken as the equilibrium contact angles, a premise supported by
the careful implementation of the sessile drop method, the lack of
change with time, and the consistency of the contact angles in replicate
measurements.
3. RESULTS AND DISCUSSION
Air−Water and Oil−Water Contact Angles. Representa-
tive images from contact angle measurements are shown in
Figure 2. The resulting contact angles for clean and silanized
surfaces are given in Table 1 and shown graphically in Figure 3.
For each surface, there are a minimum of nine replicates.
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Figure 2. Images from measurements of air−water (top row) and oil−water (bottom row) contact angles, using hexadecane as the oil. (a) Fully
water wet surface of clean silica surfaces freshly oxidized in a UV-ozone cleaner. (b) Intermediate wet surface on silica silanized by 2-
thienyltriethoxysilane. (c) Oil wet surface obtained by silanizing silica with dodecyltriethoxysilane.
Figure 3. Correlation of the oil−water and air−water contact angles
for silica and silanized-silica surfaces (diamond markers) using data
from Table 1. Excluding the fluorinated surface (square marker), the
data fit y = 1.4085x (R = 0.981, n = 13), forcing the data through the
origin.
The reported angle from the instrument for air−water experi-
ments is the air−water contact angle. However, using a drop of
hexadecane as the oil in a water matrix fluid, this instrument
reports the angle through the droplet that is complementary to
the oil−water contact angle, as shown in Figure 1. The table
reports the median, the mean, and the standard deviation of the
mean for each surface and contact angle type. The measured
values for the oil−water contact angles are reported along with
the complementary angles that represent the oil−water con-
tact angle. Throughout the tabulated results, the similarity of
median and mean values, and the small standard deviationsof
a few degrees or less for the majority of surfacesindicate the
consistency of the measured values. Data points in Figure 3 are
shown with error bars, illustrating the measured uncertainties in
the experimental values. The silanes with amino or ammonium
groups gave results that were more highly variable in the air−
water contact angle.
The selection of silanes gave surfaces that were water wet,
intermediate wet, and oil wet (see Figure 2 for examples). A
fully water wet surface with a near-zero contact angle can be
obtained by cleaning silica with either the SC1 standard clean-
ing solutions or using the UV-ozone method, provided that
contact angles were measured immediately. Silanes that create
surface residues that can participate in ionic or hydrogen
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bonding interactions with water lead to water wet or weakly
water wet surfaces; these include silanes that attach amino,
ammonium, and sulfonic acid-terminated silyl groups. At
the other extreme, the most oil wet surfaces, based on the
hexadecane−water contact angles, were obtained using silanes
that attach alkylsilyl residues to the silica. These organic
residues can interact with oils by dispersion interactions, while
having no polar interactions with water. Alkyl groups can be
attached to create oil wet surfaces using a variety of silanizing
reagents including disilazanes, trialkoxysilanes, and trichlor-
osilanes. In Table 1, dodecyl-modified surfaces gave the highest
oil−water contact angles as might be expected. Intermediate
wet, rather than oil wet surfaces, can be obtained by using
silanes that attach more polarizable organic residues than alkyl
groups. It is seen in the data that the silanes applying thiophene
residues to the surface (i.e., triethoxy-2-thienylsilane and
mercaptopropyltriethoxysilane 2-(3-trimethoxysilylpropylthio)-
thiophene) lead to intermediate wet surfaces. These reagents
provide both the larger more polarizable sulfur heteroatoms as
well as a polarizable aromatic structure leading to intermediate
wet surfaces. The more polarizable residues provide more
interaction with dipolar water than alkylsilyl residues. It has
been observed in the past that silanizing reagents that produce
oil wet surfaces may produce intermediate wet surfaces if used
at low concentrations.49 We believe that this approach is less
desirable because it relies on concentration and time for partial
molecular surface coverage, rather than achieving a final end point
surface coverage and relying on the van der Waals interaction of
the appended organic group to determine the contact angle.
Fluorinated surfaces represent a special case. Aligned close-
packed −CF3 groups on a surface are considered to yield the
lowest surface energies of solids and an upper limit of 120° for
the air−water contact angle on a smooth surface.15−17 While
known to be highly hydrophobic, fluoroalkyl-modified surfaces
are not necessarily oleophilic. Indeed, highly fluorinated sur-
faces are both hydrophobic and oleophobic.17,48,60 The experi-
mental results in Table 1 are consistent with this understanding
as the oil−water contact angle for the partially fluorinated
surface from nonafluorohexyltrimethoxysilane is lower than that
of the surfaces with aliphatic groups containing only carbon and
hydrogen atoms. Because fluorine atoms are so highly
electronegative, fluorinated alkyl groups are less able to interact
with oils by dispersion interactions than aliphatic alkyl groups.
Hence, fluorinated silanes are not ideal for creating oil wet
surfaces, even though they provide among the highest air−
water contact angles (excluding textured or superhydrophobic
surfaces).
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The measured oil−water contact angles for two cleaned
and 11 silanized surfaces that are presented in Table 1 are plotted
against the measured air−water contact angles in Figure 3
and fit to a linear correlation. The data point for the fluorinated
surface was excluded from this correlation for the reasons noted
above but is shown in the plot as a separate marker. We find an
excellent correlation between oil−water and air−water contact
angles with a slope of 1.41. This slope is similar to the ratios of
oil−water to air−water contact angles we calculated from
literature cited in the Introduction. To our knowledge, this is
the most extensive correlation of air−water and oil−water con-
tact angles for clean and silanized surfaces in the literature.
Given this correlation, one can estimate from a published air−
water contact angle whether a given silanized surface is likely to
yield a water wet, intermediate wet, or oil wet surface in terms
of the oil−water contact angle. Intermediate wet surfaces may
be expected if the air−water contact angle is in the range of
approximately 55−80°.
Theoretical Relationships. Relationships between air−
water and oil−water contact angles as their cosines, cos θwa to
the cos θow, were derived by van Dijke and Sorbie as described
in the Introduction, and the linear assumption was presented in
eq 4.35 Our own data clearly show linearity and are therefore
plotted in this form in Figure 4, giving a line with a slope of
Figure 4. Correlation of the cosines of the oil−water and air−water
contact angles for silica and silanized-silica surfaces using same data
from Table 1 as for Figure 3, exluding the fluorinated surface. The
resulting data fit is y = 0.667x + 0.384 (R = 0.981, n = 13), with an
intercept at cos θow = −1 of −0.284.
0.667 and an intercept of −0.284 at cos θow = −1. For our fluid
system with the nonspreading oil hexadecane, with values of
72.8, 52.0,41 and 27.47 mN/m for σwa, σow, and σoa, respectively,
we calculate a theoretical intercept of −0.337 at cos θow = −1
and a theoretical slope of 0.67. Our experimental slope is in
excellent agreement with theory, and the intercept is similar.
This is the first test of the theory by van Dijke and Sorbie using
a series of silanized surfaces, indicating that linearity between
cos θow and cos θwa is a reasonable assumption.
From the formulation in eq 4, it can be expected that the
slope of such a correlation for oil−water systems will depend
on the oil. The line will pass through a constant at the fully
water wet data point at one extreme (1,1), and at the other
extreme where cos θow = −1, the y value is calculated from the
oil−air, oil−water, and air−water interfacial tensions. The air−
water interfacial tension is a constant at 72.8 mN/m. For linear
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alkanes, the σow is always about 50, and the σoa values range
from about 18−28 mN/m from hexane to hexadecane. There-
fore, the slopes for the nonspreading alkanes (σoa > ∼23 mN/m)
are predicted to be in the range of 0.69−0.65. For tetrachloro-
ethylene, a nonspreading chlorinated subsurface contaminant, the
σow is 44.4 mN/m while σoa is 31.7 mN/m.23 The slope for this
nonaqueous phase liquid is therefore predicted to be 0.59, while
the intercept with cos θow = −1 is predicted to be −0.174.
Intermediate Wet Surface in a Micromodel Device.
These silanization methodologies can be applied to surfaces within
assembled pore-network micromodel structures, and contact
angles can be observed in situ where two immiscible fluids contact
each other and a linear channel side. We have previously published
an image of liquid carbon dioxide in contact with water at the edge
of an inlet area in a water wet micromodel, showing the contact
angle of 16°.43 We used borosilicate glass-covered micromodels
with silica surfaces on the pore network created by dry etch-
ing silicon followed by surface oxidation.41−43 We used similar
micromodels in the present study, and Figure 5 shows the
Figure 5. Contact angles observed within the inlet triangle region of
two micromodels, one with clean water wet silicon and glass surfaces
(27°), and the other with silanized (triethoxy-2-thienylsilane)
intermediate wet surfaces (95°). Nile red-dyed hexadecane (seen as
green in the color image) is the displacing fluid. The angles indicated
are in the nonluminescent water phase.
contact angle in a SC1 cleaned, unmodified micromodel. Because
the micromodel cover plate is attached by anodic bonding, which
occurs at temperatures as high as 400 °C, surface modification
with silanes must be carried out after the surfaces are sealed
inside the micromodel. The interior surfaces of such a model
were modified to obtain an intermediate wet surface. To load
solutions, a syringe adaptor was screwed into the inlet port and
tubing was connected to the outlet port for delivery to a waste
container. The model was flushed with 10 mL of DI water; then
30 mL of SC1 solution was passed through the micromodel for
15 min to obtain freshly cleaned surfaces. The model was rinsed
with 10 mL of DI water and dried with nitrogen gas. Triethoxy-
2-thienylsilane was slowly loaded into the model until no bubbles
were observed and caps were screwed into the ports. This
assembly was placed in an oven at 90 °C for 15 h. Finally, the
model was rinsed with 10 mL each of hexanes, DI water, and
methanol and then dried with nitrogen gas. The contact angle in
this intermediate wet micromodel can be seen in Figure 5 in
comparison with the clean water wet micromodel. A small
contact angle (27°) is observed for the water wet micromodel as
expected; the contact angle for the intermediate wet surface is
clearly different. At 95°, it is in agreement with the independently
measured value for a silica surface modified by triethoxy-2-
thienylsilane as reported in Table 1.
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4. CONCLUSIONS
This work provides a benchmark evaluation of surface wetta-
bility alteration by the silanization method and demonstrates a
linear correlation between the resulting measured air−water
and oil−water contact angles. Moreover, relating the cosines of
the air−water and oil−water contact angles, our data test the
theory from van Dijke and Sorbie35 for the first time, and we
find excellent agreement between their linear assumption and
our data. These authors strongly called for experimental work
to investigate these relationships, which are important to several
phenomena including pore occupancy and saturations in porous
media.
The silanization methodology we describe can be applied to
studies of immiscible fluid displacement across scales with
applications to important systems including geologic carbon
dioxide sequestration, enhanced oil recovery, and NAPL migra-
tion in the subsurface. We have shown how to obtain a full range
of wettabilities on silica surfaces using silanization methods,
including the identification of specific silanes to obtain inter-
mediate wet surfaces. Intermediate wet surfaces are important in
natural systems, but most experimental model systems are typi-
cally either water wet or oil wet. The sulfur-heteroatom-containing
silanes we have identified rely on the van der Waals interactions
rather than partial monolayer silanization or monolayer quality to
yield the intermediate wet surface. Silanization also represents a
covalent surface treatment in contrast to past methods that rely on
surface exposures to different fluids to obtain altered wettabilities.
For example, the exposure of water wet glass, silica, or natural
rock surfaces to liquid oils has sometimes been used to convert
them to intermediate wet or oil wet29,61−63 or lead to patterned
wettability.64
We have demonstrated the success of using silanization inside
a silicon/silica/glass micromodel device where the cover plate
has already been sealed to the surface by anodic bonding.
Additionally, we have shown that the surface modification
within a micromodel can be confirmed by an in situ contact
angle measurement. Micromodels can be fabricated by dry etching
silicon to provide extremely precise pore network structures, and
our studies suggest how such models may be used in studies at a
range of wettabilitiesnot just the wettability intrinsic to the
materials of fabrication. Wettability is a key parameter influencing
multiphase flow at the pore scale, and silanization offers a method
to enable studies at multiple interfacial energies using the same
overall micromodel technology and materials of fabrication. If used
for extended studies, the contact angles may be determined in situ
with each experiment to check that the wettability remains the
same. Silanization may also be used to alter or control wettabilities
of model (e.g., glass beads) or natural siliceous materials for multi-
phase flow studies at larger scales.
■
AUTHOR INFORMATION
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A portion of this research was carried out in the William R.
Wiley Environmental Molecular Sciences Laboratory (EMSL),
a national scientific user facility sponsored by the Department
of Energy’s Office of Biological and Environmental Research
and located at the Pacific Northwest National Laboratory
(PNNL). PNNL is a multiprogram national laboratory
operated for the DOE by Battelle Memorial Institute. The
7187
Article
Laboratory Directed Research and Development Program at
PNNL supported this research.
■
REFERENCES
(1) Abdallah, W.; Buckley, J. S.; Carnegie, A.; Edwards, J.; Herold, B.;
Fordham, E.; Graue, A.; Habashy, T.; Seleznev, N.; Signer, C.;
Hussain, H.; Montaron, B.; Ziauddin, M. Oilfield Rev. 2007, 19, 44−63.
(2) Anderson, W. G. JPT, J. Pet. Technol. 1986, 38, 1246−1262.
(3) Young, T. Philos. Trans. R. Soc. London 1805, 95, 65−87.
(4) Marmur, A. Soft Matter 2006, 2, 12−17.
(5) Marmur, A. Colloids Surf., A 1996, 116, 55−61.
(6) de Gennes, P. G. Rev. Mod. Phys. 1985, 57, 827−863.
(7) Chaudhury, M. K.; Whitesides, G. M. Langmuir 1991, 7, 1013−
1025.
(8) Zisman, W. A. Relation of the Equilibrium Contact Angle to
Liquid and Solid Constitution. In Advances in Chemistry Series, No. 43;
Fowkes, R. M., Ed.; American Chemical Society: Washington, DC,
1964; pp 1−51.
(9) Fox, H.; Zisman, W. J. Colloid Sci. 1950, 5, 514−531.
(10) Good, R. J.; Girifalco, L. A. J. Phys. Chem. 1960, 64, 561−565.
(11) Girifalco, L. A.; Good, R. J. J. Phys. Chem. 1957, 61, 904−909.
(12) Good, R. J. Theory for the Estimation of Surface and Interfacial
Energies VI. Surface Energies of Some Flurocarbon Surfaces from
Contact Angle Measurements. In Advances in Chemistry Series, No. 43;
Fowkes, R. M., Ed.; American Chemical Society: Washington, DC,
1964; Vol. 43, pp 74−87.
(13) Fowkes, F. M. Ind. Eng. Chem. 1964, 56, 40−52.
(14) Fowkes, F. M. J. Phys. Chem. 1962, 66, 382−382.
(15) Nishino, T.; Meguro, M.; Nakamae, K.; Matsushita, M.; Ueda,
Y. Langmuir 1999, 15, 4321−4323.
(16) Wong, T.-S.; Ho, C.-M. Langmuir 2009, 25, 12851−12854.
(17) Arkles, B.; Pan, Y.; Kim, Y. M. The Role of Polarity in the
Structure of Silanes Employed. In Surface Modification in Silanes and
Other Coupling Agents; Mittal, K. L., Ed.; Koninklijke Brill NV: Leiden,
2009; Vol. 5, pp 51−64.
(18) Chiquet, P.; Broseta, D.; Thibeau, S. Geofluids 2007, 7, 112−122.
(19) Chalbaud, C.; Robin, M.; Lombard, J. M.; Bertin, H.; Egermann,
P. Oil Gas Sci. Technol. 2010, 65, 541−555.
(20) Espinoza, D. N.; Santamarina, J. C. Water Resour. Res. 2010, 46,
W07537.
(21) Benson, S. M.; Cole, D. R. Elements 2008, 4, 325−331.
(22) Krevor, S. C. M.; Pini, R.; Li, B. X.; Benson, S. M. Geophys. Res.
Lett. 2011, 38, L15401.
(23) Hofstee, C.; Oostrom, M.; Dane, J. H.; Walker, R. C. J. Contam.
Hydrol. 1998, 34, 293−313.
(24) Bradford, S. A.; Vendlinski, R. A.; Abriola, L. M. Water Resour.
Res. 1999, 35, 2955−2964.
(25) Dwarakanath, V.; Jackson, R. E.; Pope, G. A. Environ. Sci.
Technol. 2002, 36, 227−231.
(26) O’Carroll, D. M.; Bradford, S. A.; Abriola, L. M. J. Contam.
Hydrol. 2004, 73, 39−63.
(27) Powers, S. E.; Anckner, W. H.; Seacord, T. F. J. Environ. Eng.
1996, 122, 889−896.
(28) Demond, A. H.; Roberts, P. V. Water Resour. Res. 1991, 27,
423−437.
(29) Buckley, J. S. Curr. Opin. Colloid Interface Sci. 2001, 6, 191−196.
(30) Buckley, J. S. Multiphase Displacements in Micromodels. In
Interfacial Phenomena in Petroleum Recovery; Morrow, N. R., Ed.;
Marcel Dekker, Inc.: New York, 1991; Vol. 36, pp 157−89.
(31) Zhao, X.; Blunt, M. J.; Yao, J. J. Pet. Sci. Eng. 2010, 71, 169−178.
(32) Dandekar, A. Y. Petroleum Reservoir Rock and Fluid Properties;
CRC Press: Boca Raton, FL, 2006.
(33) Tamai, Y.; Matsunaga, T.; Horiuchi, K. J. Colloid Interface Sci.
1977, 60, 112−116.
(34) Wei, M.; Bowman, R. S.; Wilson, J. L.; Morrow, N. R. J. Colloid
Interface Sci. 1993, 157, 154−159.
(35) van Dijke, M. I. J.; Sorbie, K. S. J. Pet. Sci. Eng. 2002, 33, 39−48.
(36) Bartell, F. E.; Osterhoff, H. J. Ind. Eng. Chem. 1927, 19, 1277−
1280.
dx.doi.org/10.1021/la204322k | Langmuir 2012, 28, 7182−7188
Langmuir Article

(37) Zhou, D.; Blunt, M. J. Contam. Hydrol. 1997, 25, 1−19.

(38) Corapcioglu, M. Y.; Fedirchuk, P. J. Contam. Hydrol. 1999, 36,
209−230.
(39) Lenormand, R. Visualization of Flow Patterns in 2D Model
Networks. In Experimental Methods in the Physical Sciences; Celotta,
R., Lucatorto, T., Eds.; Academic Press: San Diego, 1999; Vol. 35,
pp 43−67.
(40) Javadpour, F.; Fisher, D. J. Can. Pet. Technol. 2008, 47, 30−37.
(41) Zhang, C. Y.; Oostrom, M.; Wietsma, T. W.; Grate, J. W.;
Warner, M. G. Energy Fuels 2011, 25, 3493−3505.
(42) Grate, J. W.; Zhang, C. Y.; Wietsma, T. W.; Warner, M. G.;
Anheier, N. C.; Bernacki, B. E.; Orr, G.; Oostrom, M. Water Resour.
Res. 2011, 46, W11602.
(43) Zhang, C. Y.; Oostrom, M.; Grate, J. W.; Wietsma, T. W.;
Warner, M. G. Environ. Sci. Technol. 2011, 45, 7581−7588.
(44) Baumann, T.; Werth, C. J. Vadose Zone J. 2004, 3, 434−443.
(45) Werth, C. J.; Zhang, C. Y.; Brusseau, M.; Oostrom, M.;
Baumann, T. J. Contam. Hydrol. 2010, 113, 1−24.
(46) Bergslien, E. T.; Fountain, J. C.; Giese, R. Jr. Water Resour. Res.
2004, 40, W05112.
(47) Berejnov, V.; Djilali, N.; Sinton, D. Lab Chip 2008, 8, 689−693.
(48) Fadeev, A. Y. Hydrophobic Monolayer Surfaces: Synthesis and
Wettability. In Encyclopedia of Surface and Colloid Science, 2nd ed.;
Somasundaran, P., Ed.; CRC Press: Boca Raton, FL, 2006; Vol. 4,
pp 2854−2875.
(49) Menawat, A.; Joseph, H. Jr.; Siriwardane, R. J. Colloid Interface
Sci. 1984, 101, 110−119.
(50) Dawe, R. A.; Caruana, A.; Grattoni, C. A. Transp. Porous Media
2011, 86, 601−616.
(51) Shahidzadeh-Bonn, N.; Tournié, A.; Bichon, S.; Vié, P.; Rodts,
S.; Faure, P.; F., B.; Azouni, A. Transp. Porous Media 2004, 56, 209−
224.
(52) Ahmed, M. E.; Van Geel, P. J. J. Contam. Hydrol. 2009, 110, 22−
33.
(53) Jain, V.; Bryant, S.; Sharma, M. Environ. Sci. Technol. 2002, 37,
584−591.
(54) Okusa, H.; Kurihara, K.; Kunitake, T. Langmuir 1994, 10,
3577−3581.
(55) Capaccioli, S.; Lucchesi, M.; Casalini, R.; Rolla, P. A.; Bona, N.
J. Phys. D: Appl. Phys. 2000, 33, 1036−1047.
(56) Fleury, M.; Branlard, P.; Lenormand, R.; Zarcone, C. J. Pet. Sci.
Eng. 1999, 24, 123−130.
(57) Hermanson, G. T. Zero-Length Crosslinkers. In Bioconjugate
Techniques, 2nd ed.; Academic Press: San Diego, 2008; Chapter 3,
pp 215−233.
(58) Synthesis of 2-oxo-2-((3-(triethoxysilyl)propyl)amino)ethane-
sulfonic acid. In a three-neck 100 mL round-bottom oven-dried flask
sulfoacetic acid (1.0 g, 7.1 mmol) was dissolved in anhydrous DMSO
(10 mL). EDC (1.64 g, 8.6 mmol) and NHS (0.99 g, 8.6 mmol) were
added to the flask and stirred for 1 h under argon at room
temperature. APTES (1.67 mL, 7.1 mmol) was added using a syringe,
and the reaction was left to stir at room temperature for 15 h.
(59) Kern, W. Overview and Evolution of Silicon Wafer Cleaning
Technology. In Handbook of Silicon Wafer Cleaning Technology, 2nd
ed.; Reinhardt, K. A., Kern, W., Eds.; William Andrew Inc.: Norwich,
NY, 2008; pp 3−92.
(60) Wu, S.; Firoozabadi, A. Transp. Porous Media 2010, 85, 189−
213.
(61) Ferno, M. A.; Torsvik, M.; Haugland, S.; Graue, A. Energy Fuels
2010, 24, 3950−3958.
(62) Powers, S. E.; Tamblin, M. E. J. Contam. Hydrol. 1995, 19, 105−
125.
(63) Zheng, J. Z.; Behrens, S. H.; Borkovec, M.; Powers, S. E.
Environ. Sci. Technol. 2001, 35, 2207−2213.
(64) Kumar, M.; Fogden, A. Langmuir 2010, 26, 4036−4047.

7188 dx.doi.org/10.1021/la204322k | Langmuir 2012, 28, 7182−7188