WATER RESOURCES RESEARCH, VOL. 49, 47244729, doi:10.1002/wrcr.

20367, 2013

Silane modification of glass and silica surfaces to obtain equally

oil-wet surfaces in glass-covered silicon micromodel applications
Jay W. Grate,1 Marvin G. Warner,1 Jonathan W. Pittman,1 Karl J. Dehoff,1 Thomas W. Wietsma,1
Changyong Zhang,1 and Mart Oostrom1
Received 16 November 2012; revised 16 May 2013; accepted 16 June 2013; published 5 August 2013.

[1] Wettability is a key parameter inuencing capillary pressures, permeabilities, ngering

mechanisms, and saturations in multiphase ow processes within porous media. Glasscovered silicon micromodels provide precise structures in which pore-scale displacement
processes can be visualized. The wettability of silicon and glass surfaces can be modied by
silanization. However, similar treatments of glass and silica surfaces using the same silane
do not necessarily yield the same wettability as determined by the oil-water contact angle.
In this study, surface cleaning pretreatments were investigated to determine conditions that
yield oil-wet surfaces on glass with similar wettability to silica surfaces treated with the
same silane, and both air-water and oil-water contact angles were determined. Borosilicate
glass surfaces cleaned with standard cleaning solution 1 (SC1) yield intermediate-wet
surfaces when silanized with hexamethyldisilazane (HMDS), while the same cleaning and
silanization yields oil-wet surfaces on silica. However, cleaning glass in boiling
concentrated nitric acid creates a surface that can be silanized to obtain oil-wet surfaces
using HMDS. Moreover, this method is effective on glass with prior thermal treatment at an
elevated temperature of 400 C. In this way, silica and glass can be silanized to obtain
equally oil-wet surfaces using HMDS. It is demonstrated that pretreatment and silanization
is feasible in silicon-silica/glass micromodels previously assembled by anodic bonding, and
that the change in wettability has a signicant observable effect on immiscible uid
displacements in the pore network.
Citation: Grate, J. W., M. G. Warner, J. W. Pittman, K. J. Dehoff, T. W. Wietsma, C. Zhang, and M. Oostrom (2013), Silane
modification of glass and silica surfaces to obtain equally oil-wet surfaces in glass-covered silicon micromodel applications, Water
Resour. Res., 49, 47244729, doi:10.1002/wrcr.20367.

1.

Introduction

[2] Micromodels are planar microuidic devices with at

least one transparent face that enables visualization of uids within spatially structured pore networks created by
etching or other microfabrication techniques [Berejnov
et al., 2008; Buckley, 1991; Gunda et al., 2011; Javadpour
and Fisher, 2008; Karadimitriou and Hassanizadeh, 2012;
Lenormand, 1999]. Processes that are studied include, but
are not limited to, displacement of a wetting uid by an immiscible nonwetting uid (drainage), or displacement of a
nonwetting uid by an immiscible wetting uid (imbibition). For visualization in micromodels, the two uids are
distinguished from one another by their native differences
in color (e.g., when one is a dark-colored oil), by differences in refractive index (when both are clear and colorless),
Additional supporting information may be found in the online version
of this article.
1
Pacic Northwest National Laboratory, Richland, Washington, USA.
Corresponding author: J. W. Grate, Pacic Northwest National Laboratory, PO Box 999, Richland, WA 99352, USA. (jwgrate@pnnl.gov)
2013. American Geophysical Union. All Rights Reserved.
0043-1397/13/10.1002/wrcr.20367

or using colored or uorescent dyes to facilitate distinction

of two otherwise clear colorless uids [Chomsurin and
Werth, 2003; Grate et al., 2011; Lenormand, 1999]. Displacements in porous media are relevant to petroleum recovery [Abdallah et al., 2007; Buckley, 1991, 2001;
Dandekar, 2006; Zhao et al., 2010], nonaqueous phase liquid contaminant transport [Bradford et al., 1999; Demond
and Roberts, 1991; Dwarakanath et al., 2002; Hofstee
et al., 1998; OCarroll et al., 2004; Powers et al., 1996],
and geological carbon sequestration [Benson and Cole,
2008; Chalbaud et al., 2010; Chiquet et al., 2007; Espinoza and Santamarina, 2010; Krevor et al., 2011; Zhang
et al., 2011b].
[3] Wettability is a key parameter inuencing capillary
pressures, permeabilities, ngering mechanisms, and nal
saturations in displacement processes within porous media
[Abdallah et al., 2007; Anderson, 1986; Lenormand,
1999]. The wettabilities of surfaces in micromodels for
studying multiphase ow phenomena are typically dependent on the materials of micromodel fabrication. Micromodels have been developed in materials such as glass, epoxy
resins, silicon, and most recently, polydimethylsiloxane
(PDMS). Epoxy resin [Bergslien et al., 2004; Buckley,
1991; Lenormand, 1999] and PDMS models are oil-wet,
although PDMS can be treated with plasma to create a

4724

GRATE ET AL.: SILANE MODIFICATION OF GLASS AND SILICA SURFACES

When using silanes intended to yield hydrophobic oil-wet

surfaces, we have found that the resulting silica and glass
surfaces do not necessarily have the same wettabilities
even when treated under the same conditions. These differences between silica and glass represent a potential issue
for multiphase ow studies in surface-modied siliconsilica/glass micromodels, where all surfaces should ideally
have the same wettability. Glass and silica are different
materials and their surfaces change with thermal treatments
that affect surface silanol coverage. The availability of surface silanols then inuences the silanization process, the
surface density of attached organic groups, and the wettability outcome. For example, in the eld of capillary gas
chromatography, capillaries of glass, fused silica, and
quartz have all been examined and noted to have different
characteristics depending on the material, its thermal history, and the chemical pretreatments such as basic etching
or acid leaching, and these treatments inuence subsequent
silanization processes [Bartle et al., 1981; Grob, 1986].
The advantageous features of silicon-silica/glass micromodels, and the importance of wettabilities in displacement
processes, have prompted us to study the silanization of
glass surfaces in comparison with silica surfaces. Our goal
is to develop surface modication procedures that can be
applied in an anodically bonded silicon-silica/glass micromodel, where both the glass and silica surfaces of a micromodel will be similarly oil-wet.

water-wet surface temporarily [Berejnov et al., 2008; Bhattacharya et al., 2005; Javadpour and Fisher, 2008]. Glass
micromodels, typically prepared by wet etching, are waterwet [Buckley, 1991; Conrad et al., 1992; Javadpour and
Fisher, 2008; Lenormand, 1999]. The etched pore network
in the surface is sealed with either a at glass plate or a
symmetrically etched pore network in glass, creating
micromodels where all surfaces are made of the same material, and hence have the same wettability. Silicon micromodels are prepared by dry etching techniques in silicon
wafers [Chomsurin and Werth, 2003; Gunda et al., 2011;
Lenormand, 1999; Willingham et al., 2008; Zhang et al.,
2011a, 2011b], yielding structures with vertical walls and
much higher precision than wet-etched glass. The silicon
surfaces are oxidized to create a water-wet silica interface,
and the models are sealed with a borosilicate glass plate by
anodic bonding at (typically) 400 C. We will call these silicon-silica/glass micromodels. While this technique provides strongly bonded devices with near-perfect structures,
it does create models with different materials for the pore
network and the cover plate.
[4] The combination of silicon-silica and glass is normally of little consequence for obtaining micromodels of
uniform wettability so long as both surfaces are thoroughly
cleaned to provide water-wet surfaces. In our treatment, we
use the denition by Anderson [1986], where water-wet
corresponds to oil-water contact angles from 0 to 75,
intermediate-wet from 75 to 115, and oil-wet from 115 to
180 . Glass and silica surfaces can be modied with silanes
to alter the wettability, a process that is called silanization [Arkles et al., 2009; Fadeev, 2006; Grate and
McGill, 1995; Jain et al., 2002; McGill et al., 1994; Menawat et al., 1984; Shahidzadeh-Bonn et al., 2004; Wei et al.,
1993]. Alkylsilane or arylsilane reagents in the liquid form,
or adsorbed from the vapor phase, react with surface silanols to create new siloxane bonds that covalently bond the
alkyl or aryl groups to the surface, altering surface wettability. We have previously reported the air-water and oilwater contact angles obtained from diverse silanes on silica
surfaces and found a linear correlation relating these contact angles (and their cosines) [Grate et al., 2012]. This
study identied silanes that produce intermediate-wet and
oil-wet surfaces on silica, and demonstrated the surface
modication of an assembled silicon-silica/glass micromodel to obtain an intermediate-wet micromodel.
[5] Here, we turn our attention especially to the preparation of oil-wet surfaces on glass in comparison with silica.

2.

Experimental Methods

[6] In our experiments, the borosilicate glass was Pyrex

7740 obtained from Sensor Prep Services (Elburn, Ill.) and
the silica surfaces were thermal oxide grown on silicon wafer material (Virginia Semiconductor Inc., Fredericksburg,
Va.). Clean surfaces for silanization reactions on 3 cm  1
cm rectangles of silicon were obtained with a series of
water and organic solvent rinses prior to nal cleaning by
standard cleaning solution 1 for 30 min (SC1, a 7080 C
solution of ve parts deionized (DI) water, 1 part 27% ammonium hydroxide, and 1 part 30% hydrogen peroxide)
[Kern, 2008], UV-ozone [Kern, 2008] for 30 min using a
Jelight model 342 UV-ozone cleaner, concentrated nitric
acid (68%, boiling point 120 C, cleaning conditions specied in Tables 1 and 2), or aqua regia for 10 min. Surfaces
cleaned with liquid reagents were thoroughly rinsed with
deionized water. For silanization reactions, cleaned dry
samples were put in an aluminum foil lined glass jar and

Table 1. Contact Angle Measurements on Silanized Silica and Glass Surfaces Using Silanes Intended to Yield Oil-Wet Surfacesa
Contact Angles

Oil-Waterb

Air-Water

Surface Modification

Surface

Mean

Std Dev

Mean

Std Dev

Cleaning Method

Hexamethyldisilazane

Silica
Glass
Glass
Glass
Silica
Glass

97
97
96
100
102
102

2.2
1.1
2.3
1.8
1.9
1.5

9
9
9
9
9
9

140
91
114
150
148
110

4.9
3.0
2.7
3.8
4.7
2.6

9
9
9
9
9
9

UV-ozonea
Aqua regia
SC1
Boiling nitric acidc (30 min)
UV-ozonea
UV-ozone

Dodecyltriethoxysilane
a

Hexadecane is the oil.

Results on silica from our previously published work [Grate et al., 2012].
c
Concentrated nitric acid.
b

4725

GRATE ET AL.: SILANE MODIFICATION OF GLASS AND SILICA SURFACES

Table 2. Contact Angle Measurements on Simultaneously HMDS-Silanized Silica and Glass Surfaces After Various Pretreatment
Methods
Contact Angles
Thermal History
RT

Surface Pretreatment
Nitric acid, RT, 1 week

400 C


400 C

b,c,d

Nitric acid, RT, 1 week

Nitric acid, boiling, 30 min

Oil-Watera

Air-Water
Surface
Silica
Glass
Silica
Glass
Silica
Glass

Mean

Std Dev

Mean

Std Dev

101
102
100
95
95
98

1.6
1.3
0.8
1.5
2.1
2.0

9
9
9
9
9
9

154
148
152
102
140
141

2.7
1.0
3.0
5.0
7.5
2.2

9
3
9
9
9
9

Hexadecane is the oil.

RT is room temperature. The rst entry in the rst column indicates the prior thermal history of the glass.
c
Those labeled 400 C were baked at 400 C for 25 min and then cooled prior solution cleaning.
d
Concentrated nitric acid in each of these experiments.
b

the silane was drop cast over the surfaces. The jar was
closed and placed in a 90 C oven for 15 h. Samples were
solvent-rinsed with water, methanol, and hexanes after silanization and allowed to dry thoroughly before contact angle
measurements. All contact angles were determined on a
Rame-Hart Model 500 Advanced Goniometer (Netcong, N.
J.) as described in detail previously [Grate et al., 2012].
Static contact angles were stable within minutes for all
surfaces except glass surfaces modied with silanes yielding hydrophobic interfaces. The latter sometimes required
several minutes to reach stable contact angles. Measurements were typically made on three locations on each of
three samples for nine total measurements per silane/material combination.

3.

Results and Discussion

3.1. Contact Angles of Silanized Glass and Silica

Surfaces
[7] Using silanes previously identied [Grate et al.,
2012] to yield oil-wet surfaces on silica, we found that silanization reactions producing hydrophobic oil-wet surfaces
on silica do not necessarily yield oil-wet surfaces on glass.
Moreover, this may not be apparent from air-water contact
angles, which may be similar on the two materials; instead
these differences are revealed by the oil-water contact
angles. Examples collected from several experiments are
shown in Table 1. On silica, silanization with hexamethyldisilazane (HMDS) gave air-water and oil-water contact
angles of 97 and 140 , respectively, the latter of which is
clearly in the oil-wet range. However, on glass cleaned
with aqua regia prior to silanization we observed air-water
and oil-water contact angles of 97 and 91 , respectively.
The glass surface is not oil-wet by the oil-water contact
angle measurement. In a repeat experiment on glass,
cleaned with SC1, contact angles were 96 and 114 , respectively. Again, the silanized glass is not oil-wet, and again,
the oil-water contact angle on the glass is quite different
from that on silica (140 ). On the other hand, glass cleaned
in boiling concentrated nitric acid prior to silanization with
HMDS had air-water and oil-water contact angles of 100
and 150 , respectively, which is clearly in the oil-wet
range.
[8] Our rationale for using boiling concentrated nitric
acid (boiling point 120 C) was that it would act as an oxi-

dizer to thoroughly clean the surfaces, while simultaneously hydrating and cleaving surface siloxane linkages to
create a surface with abundant surface silanols for reaction
with silanes. In addition, alkali metal ions migrate to the
surface of heated glass, and these ions can be exchanged
out of the glass by acid treatment, leading to a surface
enriched in silica [Elmer, 1980; Jang et al., 2001; Wright
et al., 1980]. Wright et al. [1980] noted that leaching glass
with boiling 20% hydrochloric acid (110 C) resulted in
surfaces that were nearly pure silica, while Jang et al.
[2001] noted that boiling glass surfaces in concentrated nitric acid reduced surface concentrations of sodium, calcium, and aluminum atoms.
[9] With dodecyltriethoxysilane (see Table 1), another
silane that is expected to produce hydrophobic surfaces,
results similar to those with HMDS were observed. Airwater contact angles on silica and glass were both 102 ,
while the oil-water contact angles were 148 and 110 on
silica and glass, respectively (glass not cleaned in boiling
nitric acid). Again, the glass surface was not oil-wet; it was
quite different from the silica surface treated with the same
silane, and the difference was only apparent in the oilwater contact angle. The oil-water contact angle appears to
probe the surface differently than the air-water contact
angle, at least for the glass surfaces.
[10] The results in Table 1 were collected from experiments on glass that has been prepared for silanization by
cleaning and treatment methods, as we sought conditions to
achieve oil-wet glass surfaces. Hot concentrated nitric acid
was the most promising pretreatment method for glass to
enable silanizations leading to oil-wet surfaces. Therefore,
we set up a series of more directly comparable experiments
using the same pretreatment methods on silica and glass
surfaces followed by identical simultaneous silanization
reactions with HMDS. In these experiments, we also investigated the effect of prior thermal treatments of 400 C. Micromodels are assembled by anodic bonding at 400 C, and
therefore we needed to investigate silanizations on surfaces
with similar prior thermal histories. Results are shown in Table 2. HMDS is a monofunctional silane with regard to reactions with surface silanols. It can only bond to the surface
and not to other adjacent silanes, and thus creates a monolayer on the surface. Trichloro and trialkoxysilanes, by contrast, can bond to the surface and polymerize with one
another, potentially leading to disordered silane multilayers.

4726

GRATE ET AL.: SILANE MODIFICATION OF GLASS AND SILICA SURFACES

HMDS therefore represents a controlled test for silane without major risk of siloxane polymer formation on the surface.
[11] In the rst experiments listed in Table 2, we examined whether boiling the concentrated nitric acid was necessary. Glass and silica surfaces, with no prior 400 C
treatment, were soaked in concentrated nitric acid at room
temperature for 1 week. After silanization with HMDS, airwater and oil-water contact angles on silica were 101 and
154 , respectively, while those on glass were 102 and 148 ,
respectively. This treatment gave oil-wet surfaces with similar contact angles on silica and glass, and the results were
consistent with the prior boiling nitric acid treatment on
glass with no prior 400 C treatment as seen in Table 1 (airwater and oil-water contact angles of 100 and 150 on glass).
However, in a similar experiment where the glass was rst
baked at 400 C for 25 min before room temperature nitric
acid treatment for 1 week, silanization with HMDS produced
glass surfaces with air-water and oil-water contact angles of
95 and 102 , respectively. This glass surface is not oil-wet,
and baking the glass at high temperature clearly did have an
effect on the subsequent silanization and surface wettability
results. Heating glass at high temperature dehydrates the
glass with adjacent surface silanols condensing to form siloxane linkages. Hence, there are fewer surface silanols for
subsequent modication by the hydrophobic silane.
[12] However, when glass with a history of baking at
400 C is subsequently treated with boiling concentrated nitric acid, and then silanized, HMDS yields oil-wet surfaces
on both silica and glass. The air-water and oil-water contact
angles on silica were 95 and 140 , respectively, while those
on glass were 98 and 141 , respectively. These results with
HMDS provide a method for obtaining similar oil-wet
surfaces on silica and glass that have prior exposure to high
temperatures such as those associated with anodic bonding
of silicon-silica/glass micromodels.
3.2. Oil-Wet Micromodel
[13] Based on our studies with HMDS, we modied the
interior surface of a silicon-silica/glass micromodel that had
been assembled by anodic bonding at 400 C in our laboratories, using methods described in the supporting information.
These micromodels have been described previously [Grate
et al., 2012; Zhang et al., 2011a, 2011b]. Figure 1 compares
the displacement of water by hexadecane in micromodels
with water-wet and oil-wet surfaces. Displacements in
water-wet micromodels were described in detail previously
[Zhang et al., 2011a]. At low ow rates, displacement in the
water-wet model is unstable and is characterized by capillary
ngering with multipore blobs left undisplaced. By contrast,
hexadecane displaced water from the oil-wet micromodel
with ease, displacing the vast majority of the water with
occasional (mostly) single-pore residual water left behind.
The entry pressure for the hexadecane into the oil-wet pore
network was only approximately 50 Pa, compared to 3500
Pa in water-wet pore networks with the same pore geometry.
Figure 2 shows hexadecane and water in contact with each
other and a uid channel boundary in the entry section of the
oil-wet micromodel. The wetting of the surface by hexadecane in preference to water is apparent, and stands in contrast with similar images previously published by Grate
et al. [2012] for water-wet micromodel surfaces. The oil wet
surface was stable for at least several days as repeated dis-

Figure 1. Comparison of the displacement of water with

hexadecane in (a) water-wet and (b) oil-wet micromodels.
Micromodels and methodology were described in detail in
reference [Zhang et al., 2011a]. Hexadecane contains Nile
Red and the images were obtained by epiuorescence microscopy. Flow is from left to right at 5 L/h, corresponding average linear velocity is 2.1 cm/h.
placement experiment were performed, with alcohol rinses
to wash the model in between experiments.

4.

Discussion

[14] Our observations can be interpreted in terms of surface coverage by the silane, which varies depending on the
initial surface chemical composition of the glass. In this
interpretation, thermal histories and pretreatments leading
to lower densities of surface silanols, and hence lower densities of silane residues after reaction with HMDS, would
lead to intermediate-wet surfaces, while surfaces that yield
higher densities of silane residues after silanization would
lead to oil-wet surfaces. The oil-water contact angle is
more sensitive to these surface coverage differences than

Figure 2. Annotated uorescence microscopy image of

Nile Red dyed hexadecane (oil) in the entry region of the
micromodel, shown where the two liquid phases contact
the solid channel boundary.

4727

GRATE ET AL.: SILANE MODIFICATION OF GLASS AND SILICA SURFACES

the air-water contact angle. Some precedence for this interpretation can be found in the work by Menawat et al.
[1984], who treated soda-lime glass samples, previously
cleaned in warm nitric acid for 20 min, with various monofunctional organosilanes. Silane concentrations in liquidphase silanization reactions were varied, leading to differences in contact angles that were interpreted as differences
in surface silane coverage. The oil-water advancing contact
angles (oil used was xylene) showed large differences in
contact angle with concentration, from 70 to 100 at 0.05
mg/L silane concentration in n-hexane, up to values
approaching 160 at silane concentrations from 5 to 40 mg/
mL. Variations in air-water contact angles were not so
extreme. In one case, on increasing the t-butyldiphenylchlorosilane concentration from 0.05 to 40 mg/mL, the airwater contact angle varied from about 68 to 72 , while the
oil-water contact angle varied from 100 to 155 .
[15] In summary, in this technical note, we have demonstrated that borosilicate glass and silica surfaces do not necessarily have the same wettabilities when silanized under
the same conditions with the same silane. By nding pretreatment procedures that yield similar oil-wet surfaces on
glass and silica after silanization, even after prior exposure
to elevated temperatures (400 C), we have addressed a
practical problem that is relevant to the surface modication of anodically bonded silicon-silica/glass micromodels.
It is, in general, more difcult to obtain oil-wet surfaces on
glass after silanization, especially glass with a history of
prior high temperature treatment. In particular, we nd that
SC1 does not provide glass surfaces that yield oil-wet
surfaces after silanization. However, treatment with boiling
concentrated nitric acid does restore 400 C treated glass to
a state where it can be silanized with HMDS to yield oilwet surfaces similar to that of HMDS-silanized silica surfaces. Therefore, we generally recommend boiling with concentrated nitric acid as a treatment to prepare the interior
surfaces of silicon-silica/glass micromodels prior to silanization reactions. To prepare oil-wet micromodels with
HMDS, we specically recommend this pretreatment, and
we have demonstrated that it is feasible to do so.
[16] Acknowledgments. The Carbon Sequestration Initiative of the
Laboratory Directed Research and Development Program at the Pacic
Northwest National Laboratory (PNNL) supported this research. A portion
of this research was carried out in the William R. Wiley Environmental
Molecular Sciences Laboratory (EMSL), a national scientic user facility
sponsored by the Department of Energys Ofce of Biological and Environmental Research and located at PNNL. PNNL is a multiprogram
national laboratory operated for the DOE by Battelle Memorial Institute.

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