SPE 154228

Generation of Nanoparticle-Stabilized Emulsions in Fractures

M. R. Roberts, SPE, B. Aminzadeh, D. A. DiCarlo, SPE, S. L. Bryant, SPE, C. Huh, SPE
The University of Texas at Austin

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the Eighteenth SPE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, USA, 14–18 April 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
We investigated the ability of a dispersion of specially surface-treated nanoparticles to stabilize an oil/water emulsion of
prescribed internal structure created by flow within a fracture. We hypothesize that for a set of conditions (nanoparticle
concentration, salinity, aqueous to organic phase ratio) a critical shear rate exists. That is, for flow rates that exceed this
critical shear rate, an emulsion can be created.
Flow experiments were conducted within fractured cylinders of Boise sandstone and of Class H cement. The Boise
sandstone core (D = 1 in and L = 12 in) was cut down its length and propped open to a specific aperture with beads. The
fracture was saturated with dodecane which was displaced with nanoparticle dispersion, and vice versa while pressure drop
across the fracture was recorded. Class H cement cylinders (D = 1 in and L = 3 in) were allowed to set, then failed in tension
to create a rough-walled fracture along their length. These fractured cement cylinders were then sealed and encased in epoxy
to isolate the fractures. CT scans of the encased fractures were used to determine the aperture width, which is utilized when
calculating the shear rate inside of the fracture maintained during an experiment. A dispersion of surface-modified silica
nanoparticles and decane were co-injected into both the Boise sandstone and cement fractures and the pressure drop was
measured across the fractures at a variety of shear rates. The effluent of each experiment was collected in sample tubes.
Observation of the effluent and pressure drop data both support our hypothesis of emulsion generation being possible
once a critical shear rate has been reached. Alteration of the injected phase ratio and increased residence time of the two
phases inside of a fracture both affect the amount of emulsification occurring within the fractures. Increasing the residence
time of both phases within a fracture allows for more opportunities for emulsification to occur, resulting in a greater amount
of emulsion to be generated. Injection of high or low volumetric ratios of nanoparticle dispersion to organic phase results in
little amounts of emulsion generation; however, between the nanoparticle dispersion to organic phase ratios of 0.25:1 and 2:1
significant amounts of emulsion are generated once a critical shear rate has been reached.

Introduction
The ability of surface-modified nanoparticles to stabilize oil-in-water or water-in-oil emulsions offers a variety of oilfield
application possibilities, e.g., as mobility control and conformance control agents, and as constituents for drilling mud or well
completions cement. Much work has been done in generating, characterizing, and developing applications of, the
nanoparticle-stabilized oil-water emulsions that are known generally to have robust stability (see e.g., Binks et al., 2008), but
the use of nanoparticle-stabilized emulsions is a fairly new area of interest for oil industry (Zhang et al., 2010). In view of
their long-term stability and ability to create very low mobility, such emulsions could be very useful in blocking the fractures
often encountered in subsurface formations or those accidentally created in casing cement, especially if the emulsion can be
generated spontaneously in situ in the fracture. With such potential applications in mind, we investigated the conditions under
which surface-modified nanoparticle-stabilized oil-water emulsions can be generated inside of a rough-walled fracture.

Particle-Stabilized Emulsions. Colloidal particle-stabilized emulsions, known as Pickering emulsions, are both a hindrance
and tool for oil industry. Very stable water-in-crude oil emulsions, often encountered with produced oils, can corrode
equipment and carry solids to sensitive reactors (Sullivan and Kilpatrick, 2002). Water is sometimes emulsified in crude oil
to remove salts and fine solids. Most work on nanoparticle-stabilized emulsions has been performed within the last decade
and has focused on emulsion stability after its generation, and the factors controlling the stability, such as the contact angle
made by the oil-water interface on the particle surface, salinity, and the particle concentration (e.g., Aveyard et al., 2002).
The contact angle, or the wettability of the particle surface, is a major controlling parameter not only for emulsion stability
2 SPE 154228

but also for the emulsion strucure (oil-in-water or water-in-oil) (Binks and Rodrigues, 2007). The ability of particles to
stabilize oil-water emulsions at very low concentrations is one reason for the recent surge in interest in utilizing particles as
emulsion stabilizers. Binks and Rodrigues (2006) and Binks et al. (2010) generated stable emulsions using nanoparticle
dispersions of concentration as low as 0.1 wt%, and Zhang et al. (2010) generated stable oil-water emulsions with silica
nanoparticle concentration of as low as 0.05 wt%.

Emulsion Generation Mechanisms. For nearly all particle-stabilized oil-water emulsion studies to date, the emulsion was
generated by ultrasonically mixing the aqueous and organic phases in a batch system. Simovic and Prestidge (2004)
submerged their sample tubes in an ultrasonic bath for 2 hours. Binks and Rodrigues (2007) used Ultra-Turrax T25
homogenizer operating at 11000 rpm for 2 minutes. Similarly, Whitby et al. (2006) used a high pressure homogenizer
operating for six hours to prepare their oil-water emulsions.
The method of emulsion generation for this study is by flow shear exerted on the fluid mixture from contact with the
walls of a fracture. This is a significantly different approach than attempted by any previous study. The quantification of the
shear rate required to generate a nanoparticle-stabilized emulsion is a primary goal of this research.

Experiments on Emulsion Generation

The experiments were performed to quantify the conditions necessary to generate oil-water emulsions when an aqueous
dispersion of nanoparticles and oil flow through a fracture. We investigated three different modes of the two-phase flow: (i) a
nanoparticle dispersion displacing a hydrocarbon phase, (ii) vice versa, and (iii) their simultaneous flow by co-injection into a
fracture.

Materials. Two kinds of nanoparticles were used. One is DP 9711 silica-core nanoparticles with a nominal diameter of 20
nm, from Nyacol® (Ashland, MA). The nanoparticles were surface-modified with OH-functionality (details unavailable from
manufacturer) and received as a 30 wt% dispersion in water. At 25°C, the dispersion has a specific gravity of 1.3, viscosity of
60 cp, contains 100 ppm Na+, and is not miscible in hydrocarbon. Another is also silica-core nanoparticles with a nominal
diameter of 5 nm, from 3M® (Minneapolis, MN). The nanoparticles were surface-modified with polyethylene-glycol ligand
and received as a 41 wt% dispersion in water. For most experiments, the dispersion was diluted to 5 wt% with deionized (DI)
water. To ensure homogeneity, each diluted dispersion was stirred for 5 minutes with magnetic stirrer. The hydrocarbon
phase used for the co-injection experiments was reagent grade decane (Fischer Chemical, Fairlawn, NJ). Dodecane was used
for the displacement experiments (see below for two different flow modes).
Two types of fractures were created and used during the co-injection experiments. The first fracture was in a 12-inch
long, 1-inch diameter Boise sandstone core, cut down its length with a circular saw. The resulting model fracture was
propped with approximately one-third of a monolayer of 180 micron glass beads which were kept in place by a thin layer of
epoxy. The second type of fracture was created in a cement cylinder. Cement was chosen as the material to be fractured
because of its very low permeability and to emulate a fracture in casing cement. The cylinder was made from Class H cement
mixed with tap water, and set inside of a 1-inch diameter, 5-inch long flexible polyolefin cylindrical tube. After setting for 24
hours, the fracture was created in the cylinder lengthwise, by loading the sample in a load frame until tensile failure occurred.
The cement generally failed along its axis, resulting in a fracture through the center of the cylinder, running lengthwise from
end to end. Fracture-containing cylinders ranging in length from 3.5 inches to 1.8 inches were thus generated and used.
(Fractures generated within some cement cylinders propagated out to the side of the cylinder rather than to the opposite end;
and we used the cylinder portion for which the fracture inlet and outlet are at the cylinder’s end faces.)
The core was scanned using X-ray diffraction inside of a CT scanner. Along the entire length of the fracture, 1 mm thick
slices of the fractured cement were scanned. A map of the fracture asperity in a cement core created by tensile failure is
shown in Fig. 1. Fracture asperity was approximated using a procedure developed by Bertels et al. (2001).

Apparatus. Figure 2 is a schematic of the flow apparatus, which allows for co-injection of an aqueous dispersion of
nanoparticles and an oil phase into a fracture. The pumps used are two Series-D 1000 syringe pumps (Teledyne ISCO,
Lincoln, NE) and one Series 1500 HPLC pump (LabAlliance, State College, PA). For most experiments, the fracture was
oriented vertically, to prevent gravity segregation of fluids in the fracture. The pressure drop across the fracture was
measured using a pressure transducer (Validyne, Northridge, CA) calibrated to the estimated maximum operating pressure
(125 psi). The effluent was collected for each shear rate change.

Procedures. Two different sets of flow experiments were carried out with the cut-and-propped Boise sandstone cores. In the
first set, the fractured core was saturated with one phase, which was then displaced with the second phase at a set shear rate.
The nanoparticle dispersion used for these displacement experiments was 1 wt% 5-nm particles in 1 wt% NaCl brine. Due to
the high permeability of the Boise fracture (3.1 D), the displacing fluid had to be injected at high rates (75 and 150 mL/min)
in order to achieve shear rates we believed capable of causing emulsification. In the second set, co-injection of nanoparticle
dispersion and dodecane into the fractured core was made. The nanoparticle dispersion for the co-injection experiments was
again 1 wt% 5-nm particles in 1 wt% NaCl brine. The simultaneous injection was made at oil-to-water ratios of 4.0, 2.0, 1.2,
SPE 154228 3

0.5, and 0.25 at combined flow rates of 75, 90, and 135 mL/min. For the co-injection experiments, the core was initially
saturated with 1 wt% of NaCl.
With the rough-walled cement fracture, only the co-injection flow experiments were carried out. In order to identify the
critical shear rate for emulsification in the fracture, the mixture flow rate was increased in steps during an experiment. The
nanoparticle dispersion used was 1 wt% 20-nm particles in 1 wt% NaCl brine. For the 1:1 aqueous dispersion-to-decane
phase ratio, the mixture flow rate was increased in increments of 0.5 mL/min from 2.0 mL/min to 9.0 mL/min. The shear rate
inside of the fracture was approximately calculated using the equation for flow in a slit with a negligible height-to-width
ratio.
The effluents from the core were collected, separately for different flow rates (and corresponding shear rates), as the rate
was incrementally increased during an experiment. For every fourth flow rate run with nanoparticle dispersion and decane, an
identical experiment was run with DI water substituted for the nanoparticle dispersion. These experiments are run in order to
provide a baseline reading of pressure drop for two immiscible fluids flowing through the fracture without emulsification
occurring.
The pressure drop data acquired across each fracture was used to calculate the apparent viscosity of the injected phases as
they flow in the fracture. An increase in pressure drop from the (nanoparticle-free) baseline readings when a nanoparticle
dispersion is flowing can be interpreted to be due to generation of emulsions and their flow through the fracture.

Results
Fifty-eight flow experiments were conducted, of which 23 were with the Boise fracture and the remainder were with the
cement fracture. The effects of salinity, injected phase ratio, fracture aperture, fracture geometry, and method of injection
(displacement or co-injection) on the critical shear rate for emulsion generation were investigated.

Phase Displacement in Fracture in Sandstone. The goal of these experiments was to determine at what shear rate an
emulsion is created when a fluid phase displaces the other phase in a fracture. Table 1 lists the conditions for the 8
experiments carried out.
For Experiments D-1, D-2, D-5, and D-6, (nanoparticle-free) brine was used to displace dodecane from the fracture and
then dodecane was used to displace brine from the fracture. These experiments were performed to establish a baseline
pressure at which no emulsion was formed. Following the baseline measurements, the displacement experiments with the
nanoparticle dispersion (1 wt% 5-nm particles in 1 wt% NaCl brine, as stated in the Procedures) were performed.
Figure 3 shows the pressure drop across the fracture associated with each experiment. The first two data points at each
shear rate correspond to the flow system where no nanoparticles are present. The next two data points at the same shear rate
correspond to the flow system where nanoparticles are present. The pressure drops indicate that, even when nanoparticles
were present, no stable emulsion was generated within the fracture at the tested shear rates (5900 and 11800 s-1). This
observation was surprising given that Zhang et al. (2010) observed this nanoparticle dispersion to generate stable dodecane-
in-water emulsions at all phase ratios when a sufficient shear rate is applied. One of the reasons that a stable emulsion was
not generated in the fracture is the very short fluids-contact time in the fracture. For the shear rates of 5900 s-1 and 11800 s-1,
the contact time between the displacing and displaced fluid phases in the fracture was calculated to be 1.35 and 0.68 seconds,
respectively. While the emulsification requires a high shear rate for mixing, the two fluids appear also to need a sufficient
contact time for stable emulsion generation. During the initial contact of the two phases for Experiments D-3 and D-4, a
small amount of unstable emulsion was generated. These emulsions in the collected samples of effluent broke within minutes
after being produced.
Another reason for no emulsification may be that the viscosities of the fluids (dodecane and nanoparticle dispersion) were
too similar (approximately 1.25 and 1.1 cp, respectively) to induce viscous fingering, which would have created a large
oil/water interfacial area. Instead, the phase initially residing inside of the fracture was displaced in a near piston-like manner.
Fingering would also increase the chance of breaking off droplets of one fluid into the other; when this occurs nanoparticles
can adsorb at the fluid/fluid interface and generate stable emulsion droplets.

Co-injection into Fracture in Sandstone. Sixteen experiments were performed while co-injecting decane and nanoparticle
dispersion into the Boise fracture described in the Materials section. These experiments were designed to quantify the critical
shear rate necessary for emulsification; and study the effects on the critical shear rate of the injected oil (qo) to water (qw)
phase ratio, and salinity (CNaCl). Table 2 summarizes the experiments and their parameters. The residence time was calculated
from the estimated fracture pore volume divided by the overall flow rate. The range of residence times for the co-injection
experiments (Experiments 1-17, listed in Table 2) are nearly identical to the residence (contact) times for the displacement
experiments (Experiments D-1 to D-8, listed in Table 1). The difference between the two sets of experiments is that the
oil/water interfacial area would be much larger in the co-injection experiments, as the two phases enter the fracture already
mixed.
Except for Experiment 1 (the baseline experiment in which no nanoparticles were present in the water phase), all
experiments consisted of co-injection of decane and a 1 wt% nanoparticle dispersion. Both the 5-nm and 20-nm silica-core
particles were used. The results of these experiments are expressed in terms of the apparent viscosity, which is defined as
4 SPE 154228

nano  free o / w mixture

 app  P
Pnano  free o / w mixture

where P is the pressure drop across the fracture as the nanoparticle dispersion and decane flow through the fracture.

Effect of Injected Phase Ratio on Emulsion Generation. Five different nanoparticle dispersion-to-decane phase ratios
were tested: 4:1, 2:1, 1.25:1, 0.5:1, and 0.25:1. The apparent viscosity for each phase ratio is plotted against the shear rate for
Experiments 3 to 7, as shown in Fig. 4. For these experiments, the 3M 5-nm particles were used. The dotted line separates the
experiments that generated emulsion, as evidenced by the increase in apparent viscosity and the observation of the effluents,
from those that did not.
Some notable observations can be made. First, at a shear rate of 5850 s-1 or higher, emulsion can be generated within a
fracture (with an average aperture of 230 μm), suggesting that a certain critical shear rate is required to generate emulsions in
situ, even when the two fluids flow simultaneously in the fracture. Note that, while the contact or residence time in the
fracture for the two different modes of flow was similar, the interfacial area between the oil and water phases for the co-
injection case would be much larger than that for the displacement, as mentioned earlier. This suggests that emulsification
requires not only a large interfacial area but also a sufficient shear to bring the nanoparticles to the interface for their
adsorption.
Second, the apparent viscosity is dependent on the injected phase ratio of nanoparticle dispersion to decane. Figure 5
shows the apparent viscosity and the largest volume fraction of emulsion among the effluent samples collected, both as a
function of the phase ratio. Figure 5 shows that the trend of the apparent viscosity variation is very similar to that of the
emulsion volume fraction. This suggests that the presence of emulsion, while flowing together with the excess oil and water
phases, significantly lowers the overall mobility, a phenomenon which is also generally observed with the surfactant-
stabilized emulsions. Third, at high ratios of injected nanoparticle dispersion to decane, stable emulsion was not generated
even when subjected to a very high shear rate. For Experiments 6 and 7, emulsion was generated within the fracture but
broke after being collected (~24 hours). The effluent emulsions from Experiments 3 to 5 remained stable over six months.
The next set of experiments (Experiments 8 to 12, listed in Tables 2 and 3) was conducted using the 20-nm particles from
Nyacol. The experimental conditions including salinity, nanoparticle concentration, and the injected phase ratios were same
as those for Experiments 3 to 7. Results of the experiments using the 20-nm particles are nearly identical to the results with
the 5-nm particles and are shown in Fig. 6.

Effect of Salinity on Emulsion Generation. A third set of experiments was conducted in order to explore the effects of
higher salinity on emulsion generation within the fracture. Experiments 13 to 17 (Table 2) were performed with 20-nm
particles in 3 wt% NaCl brine, rather than in 1 wt% brine for the above experiments. The same experimental procedure was
followed as in the previous two sets of experiments. Figure 7 shows the apparent viscosity for experiments 13 to 17 as a
function of the injected phase ratio. Also plotted in the figure for comparison are the apparent viscosities of Experiments 3 to
12 from above.
The apparent viscosity response at higher salinity is nearly identical to those for the 1 wt% NaCl brine. Increased salinity,
however, somewhat increases the apparent viscosity at all phase ratios and shear rates, suggesting that the nanoparticles may
have a better affinity to the oil/water interface and more stable emulsion droplets were formed during the flow in the fracture.
This may be due to the fact that the increased electrolyte ion concentration weakens the electrostatic repulsion between
particles, allowing them to be adsorbed more densely at the oil/water interface (Zhang et al. 2010) with formation of more
stable emulsion droplets.

Co-injection into Fractured Cement. After performing experiments with artificial fractures cut in the Boise sandstone
cores, we studied the emulsion generation in fractures more representative of naturally occurring ones. Rough-walled
fractures were created in cement cylinders, similar to the fractures that may be present in the cement filling the gap between
the well casing and subsurface formation.
As summarized in Table 4, four groups of experiments were performed by co-injection into cement fracture #1, which has
an average aperture of 80 μm, almost 4 times smaller than the Boise sandstone fracture used in experimental groups 0 to 4
(Table 2). With these experiments, the shear rate requirement for emulsion generation within a fracture, and the effect of
injected phase ratio on emulsion generation, were investigated.
Experiments 18 – 21 (Group 5) were baseline experiments where decane and nanoparticle-free DI water were co-injected
into the fracture at a water-to-decane ratio of 1.0. Because no nanoparticles are present to stabilize an emulsion, no emulsion
is generated during the baseline experiments. The Group-6 experiments following the baseline experiments were carried out
at a nanoparticle dispersion-to-decane phase ratio of 1.0. Figure 8 shows the pressure drop response for shear rates from 2460
s-1 to 11070 s-1 (Experiments 22 to 36). The flow rate of each phase was increased by 0.5 mL/min for each experiment,
resulting in a shear rate increase of approximately 600 s-1 per experiment. The dashed line in Fig. 8 indicates the critical shear
rate (~7700 s-1) for emulsion generation under the conditions of the Experiments 22 to 36. Below 7700 s-1, any emulsion
generated is generally less than 5 % of the effluent volume and becomes unstable within 24 hours. Above the critical shear
SPE 154228 5

rate, the emulsion phase constitutes 20 % – 30 % of the total volume of each sample. The existence of a critical shear rate is
also confirmed by comparison of the pressure profiles of the experiments bordering the critical shear rate. Figure 9 shows the
pressure profiles of Experiments 30 and 31, with shear rates of 7400 s-1 and 8000 s-1 inside the fracture, respectively. During
Experiment 30, which is below the critical shear rate, the pressure drop remains smooth and steady while both phases are
flowing through the fracture. During Experiment 31, after the critical shear rate has been reached, a significant fraction of the
phases entering the fracture are being emulsified and are impeding flow within the fracture, creating a fluctuating pressure
profile as un-emulsified phases channel through the emulsion.

Effect of Phase Ratio on Emulsion Generation. After observing successful generation of emulsion at a nanoparticle
dispersion-to-decane phase ratio of 1.0, we tested the effect of the volumetric phase ratio on emulsion generation. Figure 10
shows the comparison of pressure drops measured for the cement fracture for nanoparticle dispersion-to-decane phase ratios
of 0.5, 1.0, and 2.0, over a range of shear rates. At phase ratios of 2.0 and 0.5, no jump in pressure drop occurs as shear rate
increases, and also significantly less emulsion volume was generated at those phase ratios. Figure 11 shows the effluent
samples of select experiments at shear rates of 3690 s-1, 6150 s-1, 8610 s-1, and 11070 s-1 for the injected nanoparticle
dispersion-to-decane phase ratios of 0.5, 1.0, and 2.0 (left-to-right, for each shear rate). Below the critical shear rate (left two
groups in Fig. 11), no stable emulsion is generated at any injected phase ratio. The white middle phase visible in the two left
groups of samples breaks within 24 hours of generation. At 8610 s-1, which exceeds the critical shear rate, a significant
decrease in emulsion volume fraction is observed for the phase ratios of 0.5 and 2.0 (right and left samples, respectively, in
each geoup) as compared to the phase ratio of 1.0 (middle sample). We measured the average emulsion droplet size (from
their microscope image and the drop size analysis software) for the above 3 phase ratios, as listed in Table 5, for two different
shear rates. The droplet size showed a minimum, opposite to the emulsion volume fraction trend, at the phase ratio of 1.0.
The cause for this behavior is unclear.

Discussions and Conclusions

Comparison of Boise Sandstone to Cement Fractures. The large decrease in the emulsion volume fraction in the effluent
from the sandstone-fracture experiments to the cement- fracture experiments is most likely due to the drastic decrease in
residence time in the fracture of the two-phase flow. At any given flow rate, the contact time inside the sandstone fracture is
17.5 times that of the cement fracture, providing more time for the two phases to emulsify with sufficient shear. The visual
observations indicate that the walls of the sandstone fracture are also rougher that those of the cement fracture.

Emulsion Generation Mechanisms. For surfactant foams and emulsions, their generation occurs easily at permeability
contrast boundaries. Tanzil et al. (2002) observed that the generation of foams by gas snap-off is significantly influenced by
the degree of permeability contrast and the gas fractional flow. In the cement fractures we generated, the spatial distribution
of its aperture is not uniform but rather patchy in some areas. It is reasonable to assume that snap off of decane droplets may
occur at these patches of aperture contrast, which correspond to areas of permeability contrast. It is also possible that a
significant amount of decane droplet snap-off is occurring at the end of the fracture, where the small aperture opens to a large
open flow channel, creating a large permeability disparity. Because the naturally generated fractures in subsurface formations
will generally have significant 2-D heterogeneity in their aperture spatial distribution, the permeability discontinuity is
believed to be an important emulsion (and foam) generation mechanism. This aspect warrants a further detailed investigation.

Conclusions
We investigated under what conditions the nanoparticle-stabilized oil-water emulsions can be generated inside of a rough-
walled fracture. Specifically, we tested the hypothesis that, to generate a stable emulsion, the shear rate inside the fracture
should exceed some critical value. For the purpose, artificial fractures were created in sandstone and cement, the fractures
were characterized, and nanoparticle dispersion and an oil phase were injected into the fractures under controlled conditions.
The effects of salinity and injected nanoparticle dispersion-to-oil phase ratio were studied over a range of shear rates.

 Displacing an aqueous dispersion of nanoparticles by dodecane, or vice versa, in a fracture does not generate
emulsion, because their almost piston-like displacement does not allow sufficient mixing between the two fluid
phases along the short (< 1 ft) distance of travel.
 Co-injection flow experiments demonstrate that the shear generated within a fracture can be sufficient to emulsify
decane into water when stabilized by a dilute (1 wt% and 5 wt%) dispersion of surface-treated silica nanoparticles.
 There exists a critical shear rate below which a stable emulsion will not be produced in a fracture. Emulsions that are
stable for more than 24 hours, for example, could not be generated with a shear rate less than 8000 s-1, under the
experimental conditions tested (in the artificial fractures in Boise sandstone and cement; and with 0 to 3.0 wt% NaCl
brine).
 For the two nanoparticles that we tested (silica-core of 5 nm and 20 nm), the particle size does not appear to have
any significant effect on the ability of emulsions to be generated by shear inside of a fracture.
6 SPE 154228

 The residence time for the two fluid phases in the fracture has a significant effect on the emulsion generation. The
more fracture area the fluid mixture is in contact, the greater amount of emulsion appears to be produced.
 The injected volumetric phase ratio has a significant effect on the emulsion generation. For the Boise sandstone
fracture, a nanoparticle dispersion-to-decane phase ratio between 0.25 and 1.25 results in a large apparent viscosity
with a sizeable volume of emulsion produced.

Acknowledgment
This material is based upon work supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy
Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
under Award Number DE-SC0001114.

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in situ saturation in a rock fracture using computed tomography scanning,” Water Resour. Res., 37(3), 649–662.
Binks, B., and Rodrigues, J. 2006. “Synergistic Interaction in Emulsions Stabilized by a Mixture of Silica Nanoparticles and Cationic
Surfactant,” Langmuir, 23, 3626-3636.
Binks, B., and Rodrigues, J. 2007. “Enhanced Stabilization of Emulsions Due to Surfactant-Induced Nanoparticle Flocculation,” Langmuir,
23, 7436-7439.
Binks, B., Kirkland, and M., Rodrigues, J. 2008. “Origin of Stabilization of Aqueous Foams in Nanoparticle-Surfactant Mixtures,” Soft
Matter, 4, 2373-2382.
Binks, B., Fletcher, P., Holt, B., Parker, J., Beaussoubre, P., and Wong, K. 2010. “Drop Sizes and Particle Coverage in Emulsions
Stabilized Solely by Silica Nanoparticles of Irregular Shape,” Phys. Chem. Chem. Phys., 12, 11967-11974.
Simovic, S., and Prestidge, C. 2004. “Nanoparticles of Varying Hydrophobicity at the Emulsion Droplet-Water Interface: Adsorption and
Coalescence Stability,” Langmuir, 20, 8357-8365.
Sullivan, A., and Kilpatrick, P. 2002. “The Effects of Inorganic Solid Particles on Water and Crude Oil Emulsion Stability,” Ind. Eng.
Chem. Res., 41, 3389-3404.
Tanzil, D., Hirasaki, G., and Miller, C. 2002. “Mobility of Foam in Heterogeneous Media: Flow Parallel and Perpendicular to
Stratification,” SPE Annual Tech. Conf., Dallas, TX. 1-4 October. SPE 78601.
Whitby, C., Djerdjev, A., Beattie, J.,and Warr, G. 2006. “Nanoparticle Adsorption and Stabilization of Surfactant-free Emulsions,” J.
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SPE Improved Oil Recovery Symp., Tulsa, OK. 26-28 April. SPE 129885.
SPE 154228 7

Table 1—Experimental plan and Results of Displacement Fracture Floods

Experiment Displacement Flow Rate Shear Rate Emulsion
Number (mL/min) (1/s) Generated
D-1 Brine > Dodecane 75 5900 No
D-2 Dodecane > Brine 75 5900 No
D-3 NP Disp > Dodecane 75 5900 No
D-4 Dodecane > NP Disp 75 5900 No
D-5 Brine > Dodecane 150 11800 No
D-6 Dodecane > Brine 150 11800 No
D-7 NP Disp > Dodecane 150 11800 No
D-8 Dodecane > NP Disp 150 11800 No

Table 2—Experimental Summary of Co-injection Experiments in a Boise Sandstone Fracture.

CNaCl qo qw  Residence
Exp Group Particles (wt. %) (mL/min) (mL/min) time (s) Emulsion
(1/s)
1 0 N/A 0 60 75 10530 0.75 No
2 1 3M 1 60 75 10530 0.75 Yes
3 2 3M 1 60 15 5850 1.35 Yes
4 2 3M 1 60 30 7020 1.13 Yes
5 2 3M 1 60 75 10530 0.75 Yes
6 2 3M 1 30 60 7020 1.13 No
7 2 3M 1 15 60 5850 1.35 No
8 3 Nyacol 1 60 15 5850 1.35 Yes
9 3 Nyacol 1 60 30 7020 1.13 Yes
10 3 Nyacol 1 60 75 10530 0.75 Yes
11 3 Nyacol 1 30 60 7020 1.13 Yes
12 3 Nyacol 1 15 60 5850 1.35 No
13 4 Nyacol 3 60 15 5850 1.35 Yes
14 4 Nyacol 3 60 30 7020 1.13 Yes
15 4 Nyacol 3 60 75 10530 0.75 Yes
16 4 Nyacol 3 30 60 7020 1.13 Yes
17 4 Nyacol 3 15 60 5850 1.35 No

Table 3—Experimental Summary of the Ratio of Effluent Emulsion to

Total Volume Ratio for Group 2 (Experiments 3-7 in Table 2)
Exp qw/qo  (1/s) Emulsion Ratio
3 0.25 5850 0.70
4 0.5 7020 0.80
5 1.25 10530 0.65
6 2.0 7020 0.10 (unstable)
7 4.0 5850 0.03 (unstable)

Table 4—Cement Fracture Experimental Summary with

Nyacol 9711 20 nm Diameter Silica Particles (Cnano Given in wt. % of Aqueous Phase)
Exp Group PR (w/o) Cnano
18 – 21 5 1.0 0
22 – 36 6 1.0 5.0
37 – 44 7 2.0 5.0
45 –52 8 0.5 5.0
8 SPE 154228

Table 5—Emulsion Droplet Size Comparison

 (1/s) PR = 0.5 PR = 1.0 PR = 2.0
D (μm) D (μm) D (μm)
8610 74 ± 13 32 ± 9 75 ± 16
11070 48 ± 11 23 ± 8 51 ± 10

25

X‐position along fracture (mm)
23
21
19
17 0.15‐0.2
15
13 0.1‐0.15
12
10 0.05‐0.1
8
6 0‐0.05
4
2
0
0
2
5
7
9
11
14
16
18
20
23
25
27
30
32
34
36
39
41
43
45
48
50
y‐position along fracture (mm)

Fig. 1—Fracture aperture map, values read in mm. The average aperture of this fracture is 80 μm. Flow is directed left to right.

Fig. 2—Schematic of fracture flood set-up: (a) syringe pump #1, (b) syringe pump #2, (c) fractured cement cylinder, (d) pressure
transducer, (e) collection point.
SPE 154228 9

5
Pressure Drop (psi)

3
5900 s‐1
2 11800 s‐1

0
0 1 2 3 4 5 6 7 8 9
Experiment Number

-1
Fig. 3—Pressure drop across the Boise fracture at two shear rates (5900 and 11800 s ) for DI water and nanoparticle dispersion
displacing dodecane and dodecane displacing DI water and nanoparticle dispersion.

2.0
1.8
1.6
Apparent Viscosity (cp)

1.4
PR = 0.25
1.2
PR = 0.5
1.0
PR = 1.25
0.8
PR = 2.0
0.6
0.4 PR = 4.0

0.2 Baseline
0.0
4000 6000 8000 10000 12000
Shear Rate (1/s)

Fig. 4—Apparent viscosity as a function of phase ratio and shear rate for Experiments 3-7 (Table 2). Points above the dotted line
correspond to emulsion observed in the effluent.
10 SPE 154228

2
App Visc
1.8
Volume Fraction of Emulsion

1.6 Vol. Fraction
Apparent Viscosity (cp)

1.4
1.2
1
0.8
0.6
0.4
0.2
0
0 1 2 3 4 5
Nanoparticle Dispersion to Decane Volume Ratio

Fig. 5—Apparent viscosity of emulsion as a function of injected phase ratio and volume fraction of emulsion generated for
Experiments 3-7 (Table 2).

2
1.8
1.6
Apparent Viscosity (cp)

1.4 PR = 0.25
1.2
PR = 0.5
1
PR = 1.25
0.8
PR = 2.0
0.6
0.4 PR = 4.0
0.2 Baseline
0
4000 6000 8000 10000 12000
Shear Rate (1/s)

Fig. 6—Apparent viscosity as a function of phase ratio and shear rate for Experiments 8-12 (Table 2).
SPE 154228 11

2
1.8
1.6
Apparent Viscosity (cp)

1.4
1.2
1
0.8 3M 1NaCl
0.6 Nyacol 1NaCl
0.4
Nyacol 3NaCl
0.2
0
0 1 2 3 4 5
Nanoparticle Dispersion to Decane Volume Ratio

Fig. 7—Salinity effect on emulsion generation by co-injection in a fracture of 230 micron aperture.

90
80
70
Pressure Drop (psi)

60
50
40
30
20
10
0
0 2000 4000 6000 8000 10000 12000
Shear Rate (s‐1)

Fig. 8—Pressure drop across the cement fracture as a function of shear rate for Group 6 (Table 4).
12 SPE 154228

Fig. 9—Pressure profiles of Experiments 30 (left) and 31 (right). #30 is below and #31 is above the critical shear rate.

80

70

60
Pressure Drop (psia)

50

40 PR = 0.5

30 PR = 1.0
PR = 2.0
20

10

0
0 2000 4000 6000 8000 10000 12000
Shear Rate (1/s)

Fig. 10—Comparison of pressure drops across cement fracture for injected phase ratios of 0.5, 1.0 and 2.0 over a range of shear
rates using 20-nm particles at 5.0 wt%.

-1 -1 -1 -
Fig. 11—Effluent samples grouped left to right by the shear rates 3690 s , 6150 s , 8610 s , and 11070 s 1, respectively. Within each
set, the left/middle/right sample is from Group 7, 6, and 8, respectively (phase ratio = 2.0, 1.0, and 0.5, respectively).