Article

Cite This: Energy Fuels 2017, 31, 11755-11764 [Link]/EF

Microencapsulation of Acids by Nanoparticles for Acid Treatment of

Shales
Robin Singh, Krishna Panthi, and Kishore K. Mohanty*
Department of Petroleum and Geosystems Engineering, The University of Texas at Austin, Austin, Texas 78712, United States

ABSTRACT: Acid treatment is one of the common well-stimulation techniques to improve the production in tight carbonates
or calcite-rich shale reservoirs. Because the reaction rates are often too large at the reservoir temperatures, retarded acid systems
such as emulsified acids, foamed acids, and polymer-gelled acids are used. The retarded acids also minimize damage to the
See [Link] for options on how to legitimately share published articles.

wellbore and propagate acids long-distance from the wellbore in fractured shales. In this work, a novel encapsulation method of
Downloaded via INDIAN INST OF TECH DELHI- IIT on September 19, 2023 at 18:10:54 (UTC).

highly concentrated acid (∼10 wt % HCl) is reported as an alternative retarded acid system. Microencapsulation of these acids is
performed using highly hydrophobic silica nanoparticles. The mixing of these particles with acid under high shear rates results in
the formation of acid-in-air powders. The release of acid from these powders could be triggered by external stimuli such as
mechanical pressure or surfactant addition. The thermal stability, corrosion inhibition efficiency, and shale surface reactivity are
compared to conventional acid-in-oil emulsions, which are typically used for shale acidization processes. The encapsulation is
found to be quite robust at 80 °C, and half-life (time taken to release 50% of encapsulated acid) is increased by more than 2
orders of magnitude as compared to acid-in-oil emulsions. A gravimetric measurement technique is used to quantify the iron
corrosion rate for these two systems. The corrosion rate for the case of powders is found to be lower than that of emulsions at all
of the studied temperatures (25, 60, and 80 °C). The shale surface topography is analyzed using an optical profilometer before
and after the surface treatment with these two encapsulated-acid systems. The release of acid from powders, triggered via
mechanical pressure, results in surface etching, which could potentially increase the fracture conductivity in shales. The release of
acid can also be enhanced by the addition of anionic surfactants in the carrier fluid. The simplicity of the acid-in-powder
generation process along with excellent thermal stability and corrosion inhibition efficiency makes the proposed acid-
encapsulation technique lucrative for acid treatment applications.

■ INTRODUCTION
Shale gas production has grown tremendously with the advent of
these fractures (without any proppants) is retained by the
nonuniform etching/roughness even after fracture closure.
modern hydraulic fracturing and directional drilling technolo- Several studies have recommended the combination of proppant
gies. Its contribution to total gas production is expected to rise HF and acid HF for effective reservoir stimulation.6,7 Although
from 34% in 2011 to 50% in 2040, indicating the important role the concept of acid HF is relatively new, other acid treatment
shale gas would play in U.S. energy future.1 Before these technologies such as downhole acidic scale removal and matrix
technologies, the production from the shale basins was not acidizing are well-established and have been widely imple-
considered economically viable. The low natural permeability of mented.8 The concept of matrix acidizing even dates back to
the shale limited the total production. The hydraulic fracturing 1895 where concentrated HCl acid was used to stimulate the
(HF) relies on the injection of nonreactive fracturing fluids such matrix of carbonate reservoirs.9
as slick water or polymeric solutions to create fractures, which One of the technical challenges associated with the
increase the contacted reservoir surface area and the stimulated implementation of acid treatment in either carbonate reservoirs
reservoir volume.2 These fracturing fluids are injected with or carbonate-rich shale reservoirs is the high reactivity of the
proppants, which maintain the fracture conductivity after fracture acidizing fluids. It leads to the face dissolution. In the case of
closure. However, there are some technical challenges associated carbonate matrix, worm holes are preferred over face dissolution.
with proppant-based HF. Notably, proppants such as sand tend In the case of shales, differential/uneven etching of the fracture
to settle vertically near the wellbore before the fracture closure face is preferred over the uniform bulk dissolution of shales and
resulting in an uneven proppant distribution.3,4 In addition to mud creation. Retarded acid systems are often used for the long-
primary fractures, HF process connects to several natural and
distance propagation of acid and creation of wormholes (in
stimulated microfractures whose fracture apertures are on the
carbonates) and differential etching (in shale fractures).
order of 0.01−1 mm. These microfractures remain inaccessible
to the proppants due to smaller aperture size as well as slow Retarded acid systems include emulsified acids (acid-in-oil
proppant transport and hence are susceptible to fracture closure. emulsions), foamed acids, and polymer or surfactant-gelled
Acid treatment after or during hydraulic fracturing (called acid acids.10−12 The acid-in-oil emulsions method is one of the most
fracturing) is an approach to improve upon HF.5 This process commonly adopted technique and offers greatest chemical
relies on the injection of reactive fracturing fluids such as
concentrated acids, which create nonuniform surface etching on Received: July 11, 2017
the fracture surface. These injected fluids can penetrate both the Revised: September 8, 2017
natural and the induced microfractures. The conductivity of Published: October 4, 2017

© 2017 American Chemical Society 11755 DOI: 10.1021/[Link].7b02003

Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

retardation.13 These emulsions are typically stabilized by a were obtained from Kocurek Industries. An anionic surfactant, Bioterge
surfactant. The presence of strong acidic conditions (pH ≈ 1) AS-40, and a nonionic surfactant, Tergitol 15-S-5, were obtained from
and harsh reservoir conditions (high temperature and high Stepan and Sigma-Aldrich, respectively. Deionized water with a
salinity) poses challenges to not only emulsion stability, but also resistivity greater than 18.2 MΩ cm was used to prepare solutions.
Iron wire with diameter 1 mm (>99.9 Fe, Sigma-Aldrich), hydrochloric
the aqueous stability of the surfactant. acid (37%, Sigma-Aldrich), and sodium chloride (Fisher Chemical)
In this work, we report a novel encapsulated acid system, were used as received.
where concentrated acids are microencapsulated using silica Encapsulation of Acids. Hydrophobic silica nanoparticles and
nanoparticles without the use of surfactants. Such particle- aqueous hydrochloric acid solution (different concentrations) were
stabilized emulsions are often referred in the literature as placed in a blender (Bella-Rocket blender) in a ratio of 1:10 by weight.
“Pickering emulsions”. Such emulsions are typically more stable The volume of the blending cup was 350 cc. The mixture was blended at
and less susceptible to coalescence than surfactant-stabilized constant speed of 16 000 rpm for 60 s using a cross-blade attachment. It
emulsions due to irreversible adsorption of nanoparticles at the resulted in the formation of water-in-air (or acid-in-air) powders with
interface.14 In these emulsions, the surface wettability of the hydrochloric acid solution completely encapsulated inside the silica
shell. These powders are referred as “acid-in-air powders” or “dry acids”
nanoparticles governs the emulsion curvature. If the nano- (analogous to “dry water”) in this Article.
particles are hydrophilic in nature, the contact angle (θ) Characterization of Encapsulated Particles. The acid-in-air
(measured through the aqueous phase) is <90°. In an air− powders were characterized using different microscopy techniques. The
water−particle system, these nanoparticles tend to stabilize air- surface morphology of the powders was characterized using scanning
in-water emulsions (aqueous foams).15 Conversely, if the electron microscopy (SEM). FEI Quanta 650 SEM operating under high
nanoparticles are hydrophobic in nature (θ > 90°), they tend vacuum at an accelerating voltage of 5 kV was used. The samples were
to stabilize water-in-air powers.16 The concept of these powders glued onto standard aluminum stubs using double-sided carbon tape.
was first introduced by Dieter et al. in 1968.17 When highly One of the drawbacks of using SEM technique to characterize water-in-
hydrophobic silica nanoparticles are blended with an aqueous air powders is that it requires vacuum during the measurement. It could
lead to water evaporation,25 which could potentially collapse the silica
solution at high shear rates, it results in the self-assembly of the shell.26 In our previous work,24 we demonstrated that the confocal laser
nanoparticles to form these water-in-air powders. The final scanning microscopy (CLSM) technique, which does not require any
product has free-flowing characteristics like a powder and a dry vacuum conditions, could be performed to characterize these powders.
appearance. Therefore, these powders are often referred as “dry Zeiss LSM 710 confocal microscope with 10× dry (EC Plan-Neofluor
water” in the literature. The process conditions required to make 10×) objective lens operating in fluorescence mode was used. The
these powders have been extensively reported.18,19 Several aqueous hydrochloric acid phase was tagged with fluorescent Nile Blue
studies have reported applications of these powders such gas A dye. The excitation wavelength for this dye was 633 nm. A small
storage in methane hydrates,20,21 heterogeneous catalysis,22 and amount of sample was placed in a chambered slide using a dropper. The
magnetically responsive fluids.23 Recently, we reported that these coverslip was placed on top to prevent any contamination and minimize
evaporation. The sample was scanned from the bottom at room
water-in-air powders could be used to encapsulate micro- or temperature. The image resolution was 1564 × 1564 pixels. The image
nanosized particles.24 The encapsulated particles could be processing was done using the open-source Fiji software.27 Optical
triggered to release the internal content based on external microscopy was performed to measure the average particle size of the
stimuli such pH and surfactants. They could be used as powders. Bright-field images of the samples were captured using a Nikon
conformance control agents in oil-field applications. optical microscope equipped with a high-resolution camera.
In this work, we focus on microencapsulation of concentrated Bulk Thermal Stability. Acid-in-oil emulsions are typically used as
acids using silica nanoparticles for a high-temperature shale acid delivery agents for stimulation of tight rocks such as shale or
acidizing process. The objective is to make the acid-encapsulated carbonate reservoirs. The stability of these conventional emulsions was
system more stable than the traditional acid emulsion system so compared to that of the acid-in-air powders formed in this work. To
form acid-in-oil emulsions, first, varying ratio of oil and acid solution
that the wellbore and near wellbore region are not exposed to containing 1 wt % Tergitol 15-S-5 surfactant were taken in glass vials.
acid; only the fractures are. We envision injecting these acid The mixtures were mixed at high shear using a rotor-stator homogenizer
encapsulating particles into hydraulic and micro fractures along (Ultra Turrax, T25, IKA Werke, Germany) operating at 10 000 rpm for
with a carrier fluid, such as oil, CO2, or water. When the pressure 30 s. The samples were then placed in ovens operating at 60, 80, and 125
is released, the fractures would try to close, which would break °C. The emulsion stability was monitored in terms of the emulsion
these particles and release acid that will etch the fracture face height (or volume) as a function of time. Similarly, the acid-in-air
unevenly. An additional option is to inject a surfactant solution in powders were also taken in glass vials and were placed under different
brine subsequently to rupture these particles. The encapsulated temperature conditions. The vials were intermittently centrifuged in a
acids can also be used for matrix acidizing in carbonate reservoirs, CRU-5000 centrifuge (Damon, Needham, MA) operating at 3000 rpm
for 2 min, and the volumes of the powder and the released acid solution
but that is outside the scope of this Article. The micro- were measured to quantify the thermal stability.
encapsulated acid product was characterized using SEM, Corrosion Rate. A gravimetric measurement technique was adopted
confocal, and optical microscopy. The release of acid was to investigate the potential corrosion inhibition benefit of encapsulating
achieved by using external stimuli such as mechanical pressure the acids.28 An iron wire of 1 mm diameter was cut into small pieces of
and surfactant addition. Complementary experiments such as length about 2.54 cm each. These pieces were cleaned with acetone to
thermal stability tests, corrosion tests, and shale topography remove any grease and then washed with deionized water. Finally, the
study were performed to elucidate the key advantages of these pieces were dried in an oven operating at 80 °C. After drying, the weight
microencapsulated acid powders over conventional acid-in-oil of each piece was measured using a sensitive weighing machine, which
emulsions. has a precision of ±0.0001 g. The pieces were immersed in different acid

■
systems for a specified amount of time, t (h). Corrosion rate was
calculated on the basis of ASTM standard.29 The corrosion rate was
METHODOLOGY calculated using the following equation:
Materials. Hydrophobic, fumed silica powder surface-treated with
K *W
polydimethylsiloxane was used. The nominal size of the primary corrosion rate (CR) =
particles was 14 nm. Calcite-rich shale core samples from Eagle Ford A*t *ρ

11756 DOI: 10.1021/[Link].7b02003

Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

where corrosion rate (CR) is in mm per year (mm y−1), K is a constant

equal to 8.76 × 104, W is mass loss in gm, A is the initial surface area in
cm2, t is the time of immersion in hours, and ρ is the density of the iron in
7.87 g cm−3.
Bulk Shale Acidization. Semidisc shaped samples were cut into
similar shape and sizes to ensure similar surface area. These samples
were dried in an oven at 60 °C overnight, and the dry weight of the
samples was measured. The samples were then placed in different acid
systems such as nonencapsulated acid, acid-in-air powders, and acid-in-
oil emulsions. (Further details about these systems will be discussed in
the Results.) The samples were then placed in an oven operating at 60
°C for 24 h. The samples were then washed with brine (4 wt % NaCl)
and again dried at 80 °C for 48 h. The difference in the dry weight (ΔM)
before and after the acid treatment was then calculated. This ΔM gives a
measure of the degree of reaction of the acid with shale samples for the
different cases. Note that in these experiments, 4 wt % NaCl was added
to the acid solutions to prevent any clay swelling in the shale.
Shale Surface Topology. The objective of the experiment was to
investigate the interaction of shale surface with the acid-in-air powders.
When concentrated acid interacts with shale surface, which is typically
enriched with minerals such as calcite, it leads to surface etching that Figure 1. (a) 5 wt % hydrochloric acid dyed with Nile Blue A (25 g); (b)
could be characterized using the surface roughness. In this work, the hydrophobic silica nanoparticles (2.5 g); (c) dry acid powder flowing
shale surface roughness was quantified using the Wyko NT9100 optical freely through glass funnel; (d) dry acid powder (total product weight =
profilometer (Veeco Instruments Inc.). Disk-shaped shale samples were 27.5 g); and (e) schematic of acid-in-air powder (white sphere
obtained by cutting shale cores (diameter: 1 in.) into pieces of 1 cm represents the silica nanoparticles).
height. These samples were initially polished using a 600-mesh
diamond-grinding plate. Two grams of dry acid powders was placed
on the shale sample. It was ensured that the initial mean surface HCl). The irregular shaped structure of these water-in-air
roughness was less than 1.1 μm. These samples were contacted with acid powder is due to jamming of particles at the interfaces. One of the
(nonencapsulated or encapsulated) for 24 h at 60 °C. (Note that in these technical limitations of performing imaging via SEM, in this case,
experiments, 4 wt % NaCl was always added to the acid solutions to is that it requires vacuum conditions during measurement, which
prevent any clay swelling in the shale.) The samples were then dried in can result in evaporation of aqueous phase and potential changes
the oven overnight. These samples were placed on a vibration-free
in the particle morphology. To address this concern, we
platform of the profilometer and were scanned in the vertical scanning
interferometry mode in a noncontact manner. performed imaging analysis using confocal laser scanning
Surfactant-Triggered Release. In our previous study,24 we microscope and an optical microscope, which does not require
reported that micro- or nanosized particles could be encapsulated any vacuum conditions. As mentioned above, the acid phase was
using water-in-air powders. We showed that these encapsulated particles tagged with a fluorescent dye (Nile Blue A) before the dry acid
could be released using different stimuli such as a change in surfactant formation. Although, postencapsulation, the acid phase in
concentration or change of the pH medium of the external carrier fluid. enclosed within the silica shell, the CLSM technique could still
Following a similar approach, we studied the delayed release of acid from image the encapsulated fluorescent material. Carter et al.26 first
acid-in-air powders using a surfactant in this work. One gram of dry acid demonstrated this technique to image the “dry water emulsion”
powders was mixed with 4 g of deionized water in centrifuge tubes. formed in their study. Figure 2b shows the confocal micrograph
These tubes were placed in the oven operating at 60 °C. A small amount
of sample was collected from the vials and was analyzed using ion
of the dry acid powder with fluorescent acid phase shown in
chromatography (IC) for chloride ion to quantify the release of acids magenta (pseudocolor). Figure 2c shows the optical micrograph
from the powders. of the same sample. The average particle size of the powder was

■
measured to be 27 ± 12 μm.
Formation of Acid-in-Oil Emulsions. Injection of a strong
RESULTS
acid into a reservoir has two disadvantages: unwanted interaction
Formation of Acid-in-Air Powders. First, 25 g of with the wellbore and too fast reaction with the rock matrix. To
concentrated hydrochloric acid (5 wt %) was taken in the minimize these two issues, acid-in-oil emulsions are typically
blending cup. The aqueous solution was mixed with a small used as delivery vehicles. The slow breaking of these water-in-oil
amount of hydrophilic, fluorescent Nile Blue A dye (3 drops of 1 type emulsion ensures long distance propagation of acids. The
wt % stock dye), as shown in Figure 1a. The aqueous solution was first step in obtaining acid-in-oil emulsions is to choose a suitable
mixed with 2.5 g of hydrophobic silica nanoparticles (Figure 1b) surfactant. The radius of the curvature of oil−water interface is
in the cup. The mixture was blended at 16 000 rpm for 60 s. It governed by head and tail components of the surfactant
resulted in the formation of acid-in-air powders. The appearance stabilizing the interface.30 The HLB (hydrophile−lipophile
of this powder is completely dry (Figure 1d), and it flows freely balance) of surfactant determines the tendency of the surfactant
through a glass funnel (Figure 1c), indicating a dry powder-like monolayers to curve toward either the water or the oil phase
behavior, albeit it is a 90% aqueous solution by weight. The final resulting in water-in-oil emulsions or oil-in-water emulsions.31,32
product, termed here as dry acids, looked white in color (Figure Typically, a surfactant with HLB range of 7−11 acts as a water-in-
1d), indicating the complete encapsulation of blue acid solution, oil emulsifier while an HLB range of 12−16 acts as an oil-in-water
as shown in schematic Figure 1e. emulsifier. Therefore, in this work, Tergitol 15-S-5 was chosen
The obtained dry acid powder was characterized using several whose HLB is 10.5 per the vendor. Decane was used as the oil
analytical techniques. First, the external morphology of the phase in this work, but most oils would work as well.
powder was characterized using scanning electron microscopy Concentrated acid (5 wt % HCl) with 1 wt % Tergitol surfactant
(SEM). Figure 2a shows the SEM image of the dry acid (5 wt % and decane were taken in a vial in the ratio of 70:30 as shown in
11757 DOI: 10.1021/[Link].7b02003
Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

Figure 2. (a) SEM image of the acid-in-air powders (scale bar is 50 μm); (b) confocal micrograph of acid-in-air powders with acid phase dyed using Nile
Blue A dye (scale bar is 200 μm); and (c) optical micrograph of acid-in-air powder (scale bar is 100 μm).

Figure 3. (a) Vial containing acid solution (5 wt % HCl) containing 1 wt % Tergitol surfactant dyed with Nile Blue A and decane before mixing; (b)
texture of acid-in-oil emulsions after mixing; (c) vial containing acid solution (5 wt % HCl) containing 1 wt % Bioterge surfactant dyed with Nile Blue A
and decane before mixing; and (d) texture of oil-in-acid emulsions after mixing. Some foam is also present on the top of the emulsion.

Figure 3a. A small amount of hydrophilic dye, Nile Blue A, was homogenizer at 10 000 rpm for 30 s. The stability of the emulsion
added to the aqueous acid phase for visualization. The acid−oil was measured in terms of relative emulsion height as a function of
mixture was mixed vigorously using a homogenizer (Ultra- time. Relative emulsion height is the ratio of height (or volume)
Turrax T25) operating at 10 000 rpm for 30 s. It resulted in the to the initial emulsion height just after mixing. A higher emulsion
formation of the acid-in-oil emulsion, as shown in Figure 3b. The height indicates slower release of acid via bubble coalescence.
emulsion texture was white in color (as opposed to blue), Figure 4a−c shows the plot of decay of emulsion height with
indicating the complete encapsulation of blue aqueous phase as time for the three temperatures. The half-life of the emulsion, a
shown in the schematic in Figure 3b. For visual comparison, measure of bulk emulsion stability, defined as the time taken for
another surfactant, Bioterge, was chosen whose HLB was >12. As the emulsion to break into one-half of its original height can be
in the previous case, the concentrated acid (5 wt % HCl) with 1 calculated corresponding to relative emulsion height of 0.5 from
wt % Bioterge surfactant and decane were taken in a vial in the the plot. The half-life was more than 180 h for 50% quality
ratio of 70:30 (Figure 3c). The same amount of dye was added to (volume fraction of acid) at 25 °C, indicating a stable emulsion.
the aqueous phase. Figure 3d shows the emulsion texture after The half-life was <2.5 h for the 70% and 90% cases at 25 °C. As
homogenization at 10 000 rpm for 30 s. The emulsion is blue in expected, the emulsion stability decreases with an increase in
color, indicating oil-in-acid type emulsion as shown in the temperature. The half-lives were 1.3, 2.7, and 0.5 h
schematic. Therefore, Tergitol surfactant was chosen to form corresponding to 50%, 70%, and 90% quality at 60 °C. They
acid-in-oil emulsions in the subsequent experiments. were 0.9, 1.16, and 0.4 h corresponding to 50%, 70%, and 90%
Thermal Stability. The thermal stability of the encapsulated quality at 80 °C. The lower half-lives at higher temperature
acid system is critical for the successful implementation of the indicate a weaker emulsion. The outer liquid (oil here) drainage
shale acidization process. A stable system will ensure long process increases with an increase in temperature due to a
distance propagation of the acid in the fractures and avoid reduction in viscosity, which results in a thinning of the lamellae
localized dissolution. Moreover, it will minimize corrosion and an increase in coalescence tendency of the emulsion.
damage to surface equipment and the wellbore. The thermal Similarly, the bulk thermal stability of the acid-in-air powders
stability of both acid-in-oil emulsion and the acid-in-air powder was studied. The acid concentration was kept the same as in the
was conducted at 25, 60, and 80 °C. The acid concentration was previous case and equal to 5 wt %. The powder was prepared by
kept constant at 5 wt %. For the case of an acid-in-oil emulsion, mixing nanoparticles and acid solution in the ratio of 1:10 by
three different qualities (volume fraction of acid), 50%, 70%, and weight and was kept in ovens operating at three different
90%, were investigated. The acid−oil mixture was mixed using temperatures. Analogous to the emulsion case, the stability of
11758 DOI: 10.1021/[Link].7b02003
Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

Figure 4. Relative emulsion height of the acid-in-oil emulsions as a function time at (a) 25 °C, (b) 60 °C, and (c) 80 °C. (d) Relative powder height of
acid-in-air powders as a function of time for three temperatures.

these powders was evaluated on the basis of the relative powder The compartmentalization of acids in either powder or
height (or volume) with time. To quantify the released acid emulsion forms reduces the direct contact of the acid with the
accurately and ensure there is no trapped released acid in the external solid surface, which could reduce the corrosive effect of
powders, the vials were taken out of the ovens periodically and acid. This experiment was conducted at 60 °C. The chosen acid
were centrifuged at 3000 rpm for 3 min. Figure 4d shows the concentrations were 1, 5, and 10 wt %. Three different cases were
decay of powder height with time. Interestingly, the acid-in-air studied. In the first case, iron samples were submerged in acid
powders were found to be quite stable at all temperatures. The directly (referred here as nonencapsulated acid) and were placed
half-lives were greater than 200 h for the three temperatures. The in the oven for a fixed amount of time. In the second case, the
powder height was only reduced to 94.5%, 83.5%, and 84.0% iron samples were placed in the acid-in-oil emulsions. The quality
(from 100% initial volume) in 200 h corresponding to 25, 60, and of emulsion was kept constant at 50%. Finally, in the third case,
80 °C, indicating minimal release of acid from the system and the iron samples were placed in the acid-in-air powders. The total
relatively stable acid system as compared to acid-in-oil emulsions. amount of acids was kept constant in all three cases. Figure 5a−c
Note that the half-lives were increased from a few hours for shows the corrosion rate for the three different acid
emulsions to more than 200 h for acid-in-air powders at 60 and concentrations at three different temperatures. At every
80 °C. The higher stability of these particle-stabilized emulsions temperature, the highest corrosion rate was found for the
(powders) is due to the irreversibly adsorbed nanoparticles at the nonencapsulated acid case for all of the acid concentrations. The
air−water interface, which act as a physical barrier between two corrosion rate was relatively reduced for the case of acid-in-oil
acid droplets, thus retarding the droplet coalescence process.33 emulsions for all of the cases. For example, it was reduced from
Corrosion Rate. One of the challenges associated with acid 3121.9 to 136.8 mm y−1 (reduction factor of 22.82) for the case
stimulation is to prevent corrosion of wellbore and surface of 5 wt % acid concentration at 60 °C. In all of the cases, the acid-
equipment due to contact with the acid. Emulsification of the in-air powder outperformed the acid-in-oil emulsion with a
acid in oil helps reduce this reaction. Different types of acids are reduction in corrosion rate. For example, the corrosion rate for 5
used for stimulation purposes in carbonates and shales. These wt % acid case at 60 °C was only 31.6 mm y−1, which is a
include HCl, HF, nitric acid, acetic acid, and formic acids.34 reduction from 136.8 mm y−1 for the emulsion. These data
However, the most common acidizing agent is HCl with high showcase the potential of acid-in-air powders to minimize
concentrations of 5−28%.35 Therefore, in this work, we chose corrosion damage to the wellbore equipment.
HCl to evaluate the corrosion of iron. We investigated the degree Bulk Shale Acidization. The goal of this experiment was to
of corrosion of an iron wire due to HCl acid, conventional acid- understand the degree of interaction between the acid and the
in-oil emulsions, and acid-in-air powders. mineral present in shale samples. It was quantified by measuring
11759 DOI: 10.1021/[Link].7b02003
Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

Figure 5. Corrosion rate for different acid systems at (a) 25 °C, (b) 60 °C, and (c) 80 °C.

the weight loss of the shale sample. Four different cases were
studied. These include direct reaction with HCl acid (referred
here as nonencapsulated acid), acid-in-air powders (crushed and
uncrushed), and acid-in-oil emulsions. These experiments were
performed at 60 °C, and the reaction period was 24 h for each
case. Three different HCl acid concentrations, 1, 5, and 10 wt %
were used. Because the permeability of the shale samples is very
low, the acid reaction is strongly controlled by the exposed
surface area. Therefore, all of the shale samples were cut in similar
size and shape to ensure similar surface areas. In the first case, the
shale samples were submerged in concentrated acid (1,5, and 10
wt %) at 60 °C for 24 h. The shale samples were then taken out
and were dried in an oven at 80 °C overnight. The % mass loss in
the shale sample was calculated and is plotted in Figure 6. As
expected, the percentage mass loss increases with an increase in
acid concentration. It was 3.8%, 18.0%, and 21.7% corresponding
to 1, 5, and 10 wt % acid concentrations. In the second case, shale
samples were submerged in the acid-in-oil emulsions with acid
Figure 6. Percentage mass loss of the shale samples for acid systems with
concentrations of 1, 5, and 10 wt %. The quality of the emulsion varying concentrations.
was kept constant at 50%. The percentage mass loss, in this case,
was very close to the nonencapsulated acid case as shown in
Figure 6. It is due to the poor stability of the acid-in-oil emulsion encapsulated acid concentrations. This shows that, as observed in
as observed in the bulk stability experiments. In the third case, the cases of corrosion study, the acid encapsulation via the acid-
shale samples were placed in three different acid-in-air powder in-air powders is quite robust, and the interaction between the
systems. The concentrations of encapsulated acid were 1, 5, and acid and the shale surface is small. Finally, in the fourth case, the
10 wt %. No external pressure or stimuli were applied to release shale samples were again placed in acid-in-air powders with
the encapsulated acid in this case. The objective was to varying acid concentrations (1, 5, and 10 wt %). However, in this
investigate the interaction between shale samples and any case, the whole system was pressed using a Teflon-coated plate to
spontaneously released acids. Figure 6 shows that the mass loss crush the acid powders (to mimic the fracture closure) and
was only 0.4, 1.1, and 4.6 wt % corresponding to 1, 5, and 10 wt % release the encapsulated acid. The system was placed in an oven
11760 DOI: 10.1021/[Link].7b02003
Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

Figure 7. Shale surface topology (a) of the original shale sample; (b) polished shale sample; and after treatment with (c) nonencapsulated acids, (d)
acid-in-oil emulsions, (e) acid-in-air powders (uncrushed), and (f) acid-in-air powders (crushed).

at 60 °C for 24 h. The mechanical pressure released the surfaces of these samples were quite rough due to scratches from
concentrated acid, which reacted with the shale surfaces. The the cutting saw, as shown in Figure 7a. The blue regions
mass loss, in this case, was quite similar to that of the represent the valley regions, whereas the red regions represent
nonencapsulated acid case (Figure 6), indicating that the silica the elevated regions. The average and root-mean-square
nanoparticles did not interfere with the reaction and most of the roughnesses were 4.76 ± 1.18 and 6.10 ± 1.37 μm, respectively.
acid was released. This experiment shows how acid-in-air Therefore, all of the samples were first polished using a 600-mesh
powders can act as carrier agents for concentrated acid. The diamond-grinding plate to smoothen the surfaces to ensure
reaction of acids with shale surface would be considerably repeatability of the experiments. The average roughness of the
retarded when no external stimuli such as mechanical pressure samples was reduced to 1.02 ± 0.22 μm. Figure 7a and b shows a
were applied. The fracture closure will result in the instant release direct comparison between the same shale sample before and
of acid, which will result in surface-etching and increased fracture after the polishing. Four different cases were investigated. An acid
conductivity after fracture closure. resistant O-ring was first placed on the shale samples, and
Shale Surface Topology. The parameters average rough- different acid samples were placed on the shale. In the first case,
ness (Ra) and root-mean-square roughness (Rrms) are typically (nonencapsulated) acid (5 wt %) HCl was placed on the shale
used to quantify the roughness of any surface. The original sample. It was pressed with a Teflon sheet using a steel clamp.
11761 DOI: 10.1021/[Link].7b02003
Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

The O-ring prevented any leakage of acids and evaporation. The nature of the silica nanoparticles. Any external stimuli such as an
system was placed in an oven operating at 60 °C for 24 h. The increase in pH that can alter the surface wettability of these
shale samples were then washed with brine (4 wt % NaCl) and particles toward hydrophilicity can weaken the acid-in-air
were dried at 60 °C overnight. The surface topography was then powder.24 A surfactant molecule, comprised of the hydrophilic
performed. Figure 7c shows the result of one of the scans. The tail and hydrophobic chain, can physically adsorb on the silica
average roughness of the shale sample increased to 4.32 ± 1.37 nanoparticles to make the surface water-wet. In this work, acid-
μm. A comparison between Figure 7b and c shows the etching of in-air powders were mixed with an aqueous solution of an anionic
the shale surfaces with blue regions, indicating the valleys/etched surfactant, and the vials were placed in the oven operating at 60
regions in the acid treated shale (Figure 7c). °C. A small amount of aqueous sample was taken intermittently
In the second case, a small amount of acid-in-air emulsion was to measure the amount of released chloride ions using ion
placed on the shale sample with the help of acid-resistant O-ring, chromatography, which gives the measure of the amount of acid
and a Teflon plate was placed on it and the system was slightly released with time. Figure 8 shows the plot of the percentage
tightened using a clamp to prevent any leak of the emulsion.
Figure 7d shows the shale topography for this case. The average
roughness, in this case, was 3.77 ± 0.60 μm, much higher than in
the base case, indicating release of acid from emulsions. Similarly,
a small amount of acid-in-air powder was placed on the shale
samples using the O-ring, and a Teflon sheet was clamped to
prevent any leakage. However, the system was not fully tightened
in this case. The system was placed in an oven at 60 °C for 24 h.
Figure 7e shows the surface topography of the shale sample. The
average surface roughness was measured to be 1.19 ± 0.05 μm,
which is close to the initial average surface roughness of the
polished plates indicating no spontaneous release of acid at 60
°C. This result is in line with the thermal stability results, which
showed that the acid-in-air powders show excellent stability even
at temperatures as high as 80 °C. In the fourth case, the same
procedure was repeated, and acid-in-air powders were placed on
the sample. However, in this case, the clamp was fully tightened,
which resulted in crushing of the powders and thus releasing the
acid. The presence of the O-ring prevented the leak of the Figure 8. Percentage release of the encapsulated acid from the acid-in-
released acid. Figure 7f shows the surface topology of the shale air powders with external aqueous fluid with surfactant concentrations of
sample for this case. The surface etching is clearly visible on the 1, 0.1, 0.05, and 0.01 wt %.
shale surface, confirming the release of the acid. The surface
roughness, in this instance, was 3.72 ± 0.87 μm. All of the
roughness results are listed in Table 1. Both average roughness release of acids with time. The total amount of acid released was
and RMS roughness followed a similar trend. Table 1 normalized using the maximum amount of acid present in the
summarizes the average and RMS roughnesses for all of the system. For the case of 1 wt % surfactant, all of the encapsulated
cases studied. acid was released within 10 min. The t50, time taken for the 50%
of acid release, was 3.5, 438.2, 3625.6, and 4146.7 min for 1, 0.1,
Table 1. Average and Root Mean Square Roughness of the 0.05, and 0.01 wt % surfactant solutions, respectively. The degree
Shale Samples of acid release was reduced with a reduction in the surfactant
concentration. In our previous work,24 a contact angle study was
average roughness, rms roughness,
label cases Ra, μm Rrms, μm reported using highly hydrophobic glass slides as a proxy for
a unpolished 4.76 ± 1.18 6.10 ± 1.37
hydrophobic silica nanoparticles. It was shown that an increase in
b polished 1.02 ± 0.22 1.52 ± 0.24
the concentration of surfactant in the aqueous solution reduces
c nonencapsulated acid 4.32 ± 1.37 6.17 ± 1.90
the air−water contact angle (measured through water phase),
d acid-in-oil emulsion 3.77 ± 0.60 5.00 ± 0.57
making the surface increasingly hydrophilic. Thus, by selecting
e acid-in-air powders 1.19 ± 0.05 1.64 ± 0.09
the concentration of surfactant in the external aqueous carrier
(uncrushed) fluid, a delayed release of acid can be achieved before the fracture
f acid-in-air powders 3.72 ± 0.87 5.06 ± 0.98 closure. Because the physical adsorption of surfactant on
(crushed) nanoparticles’ surface governs the emulsions-breaking process
and the release of acids, the surfactant type will play a major role
Surfactant-Triggered Release. In the previous section, the in controlling this release rate. Future studies will explore the
acid release from acid-in-air powders was triggered using effect of different surfactant types on the rate of release of acids.
mechanical pressure. During the acid treatment process, the Nevertheless, it is to be noted that, postfracture closure,
fracture closure pressure is typically very high (order of mechanical crushing is expected to be the dominating
thousands of psi), which will result in mechanical crushing of mechanism for the complete release of acids.
powders and complete release of encapsulated acids. An Comparison with Other Acid Treatment Processes. In
additional strategy for the controlled-release of acids before the acid treatment, direct injection of acids is avoided as it can cause
fracture-closure can be achieved by the addition of surfactants to several operational issues. Notably, it leads to corrosion of
the aqueous-based carrier fluid transporting the powders. The wellbore and results in precipitation of iron-containing
formation of acid-in-powders relies on the hydrophobic wetting compounds, which will require the addition of corrosion
11762 DOI: 10.1021/[Link].7b02003
Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

inhibitor and iron-sequestering agents. Moreover, it will lead to

excessive reaction near wellbore regions. To avoid these issues,
retarded acid systems such as emulsified acid system or solid
encapsulated acid system are typically used. Both of these
systems have their own drawbacks. Although emulsified acids
have been successfully used in some fields, robust emulsion
stability is still a challenge, and it requires additional additives and
specialized equipment and expertise.36 In this article, the key
advantages of proposed acid powders over acid-in-oil emulsions
were illustrated in terms of stability tests and corrosion tests.
The solid encapsulated system relies on physical or chemical
degradation of the surface coating for the release of acid. The
precise control of required chemical conditions in the reservoir is Figure 9. Sketch of a possible application of acid-in-air powders in shale
difficult. Moreover, bulk scale production of these coated systems fractures.
is prone to physical defects, which will lead to early release of
acids. For example: Burgos et al.37 reported a field trial of acid
fracturing using encapsulated citric acid. The acid was coated
with vegetable oil, which prevented mixing with aqueous carrier (2) Acid-in-oil emulsions were formed by choosing a
fluids. The system relied on melting of coating above 180 °F in surfactant with HLB of 10.5 with the inner phase of concentrated
reservoir and crushing during fracture closure. Similarly, Nasr-El- acid (1−10 wt %) and a continuous external phase of decane oil.
Din et al.38 reported the injection of the precursor of lactic acid in (3) The acid-in-air powders show excellent thermal stability as
the form of solid beads. These beads hydrolyze in the presence of compared to acid-in-oil emulsions with 2 orders of magnitude
water and produce in situ lactic acid. One of the reported higher half-lives (time taken to release 50% encapsulated acid) at
operational challenges encountered during the implementation 60 and 80 °C.
was that not all of the beads were hydrolyzed due to an (4) The corrosion inhibition capability of these powders was
insufficient amount of water as most of the water was leaked-off superior to acid-in-oil emulsions or nonencapsulated acid. It
in the formation after the fracture closure. The proposed acid makes them lucrative to use in subsurface applications as it will
powders technique does not need any such reaction conditions reduce corrosion damage to surface equipment and wellbores.
for the release of acids and thus are more robust. Also, as opposed (5) Shale topography study reveals release of acid from the
to a reaction-based coating, the coating in the acid powders relies acid-in-air powders when the external stimulus of external
on self-assembly of silica nanoparticles at the air−water interface pressure was applied. The released acid resulted in surface
and therefore are not susceptible to physical coating defects. etching and an increase in average surface roughness of the
Moreover, the one-step method of formation of acid powders sample. Such roughness in the walls of primary fractures or
offers a facile route for bulk scale production of these powders. microfractures could potentially enhance the productivity of
The dry acid powder used in this study was formed using a shale reservoirs.
nanoparticle to acid solution mass ratio of 1:10. Thus, 1 lb of dry (6) The release of acid from the acid-in-air powders could be
acid powder will require 0.091 lb of nanoparticles. Assuming a triggered by adding a small amount of surfactant in the carrier
nanoparticle cost of about $5 per lb, the additional nanoparticle fluid. The percentage release increases with an increase in the
surfactant concentration.

■
cost would be $0.45 per lb of dry powder. These preliminary
results for the acid powder systems are quite promising. In the
AUTHOR INFORMATION
future, detailed reservoir specific studies must be performed to
fully understand the technical, operational, and financial Corresponding Author
challenges. *Tel.: (512) 471-3077. Fax: (512) 471-9605. E-mail: mohanty@

■
[Link].
ORCID
CONCLUSIONS
Robin Singh: 0000-0001-9644-1086
A simple one-step approach for encapsulation of concentrated Kishore K. Mohanty: 0000-0002-6658-2651
acids was reported using nanoparticles. Highly hydrophobic silica
Notes
nanoparticles were mixed with concentrated HCl acid at high
The authors declare no competing financial interest.

■
shear rates to obtain acid-in-air powders. These powders can act
as robust acid encapsulating agents, and the acid-release could be ACKNOWLEDGMENTS
triggered using external stimuli such as mechanical pressure or
surfactant addition.39 Figure 9 shows a sketch of a possible We are thankful to the sponsors of Gas EOR Industrial Affiliates
application of acid-in-air powders in shale fractures. In the field Project at The University of Texas at Austin for partial funding of
this work.

■
conditions, the air can be substituted by any aqueous (brine) or
nonaqueous fluids (e.g., diesel, crude oil, NGL, and natural gas). REFERENCES
Thermal stability, corrosion inhibition efficiency, and shale
surface reactivity were compared to conventional acid-in-oil (1) Outlook, A. E. DOE/EIA-0383; Department of Energy. Energy
Information Administration: Washington, DC, 2001.
emulsions, which are typically used for shale acid treatments. The (2) Guo, T.; Zhang, S.; Qu, Z.; Zhou, T.; Xiao, Y.; Gao, J. Experimental
following conclusions can be drawn from this work: Study of Hydraulic Fracturing for Shale by Stimulated Reservoir
(1) Microencapsulation of concentrated HCl acid (1, 5, and 10 Volume. Fuel 2014, 128, 373−380.
wt %) was successfully performed by forming acid-in-air powders (3) Tong, S.; Mohanty, K. K. Proppant Transport Study in Fractures
using highly hydrophobic silica nanoparticles. with Intersections. Fuel 2016, 181, 463−477.

11763 DOI: 10.1021/[Link].7b02003

Energy Fuels 2017, 31, 11755−11764
Energy & Fuels Article

(4) Tong, S.; Singh, R.; Mohanty, K. K. Proppant Transport in (25) Forny, L.; Pezron, I.; Saleh, K.; Guigon, P.; Komunjer, L. Storing
Fractures with Foam-Based Fracturing Fluids. SPE Annual Technical Water in Powder Form by Self-Assembling Hydrophobic Silica
Conference and Exhibition, San Antonio, Texas, SPE-187376-MS, 2017. Nanoparticles. Powder Technol. 2007, 171 (1), 15−24.
(5) Grieser, W. V.; Wheaton, W. E.; Magness, W. D.; Blauch, M. E.; (26) Carter, B. O.; Weaver, J. V. M; Wang, W.; Spiller, D. G.; Adams, D.
Loghry, R. Surface Reactive Fluid’s Effect on Shale. Production and J.; Cooper, A. I. Microencapsulation Using an Oil-in-Water-in-Air “dry
Operations Symposium, SPE-106815-MS, 2007. Water Emulsion. Chem. Commun. 2011, 47 (29), 8253−8255.
(6) Bale, A.; Smith, M. B.; Klein, H. H. Stimulation of Carbonates (27) Schindelin, J.; Arganda-Carreras, I.; Frise, E.; Kaynig, V.; Longair,
Combining Acid Fracturing With Proppant (CAPF): A Revolutionary M.; Pietzsch, T.; Preibisch, S.; Rueden, C.; Saalfeld, S.; Schmid, B.; et al.
Approach for Enhancement of Final Fracture Conductivity and Effective Fiji: An Open-Source Platform for Biological-Image Analysis. Nat.
Fracture Half-Length. SPE Annual Technical Conference and Exhibition, Methods 2012, 9 (7), 676−682.
SPE-134307, 2010. (28) Salarvand, Z.; Amirnasr, M.; Talebian, M.; Raeissi, K.; Meghdadi,
(7) Li, W.; Oliveira, H. A.; Maxey, J. E. Invert Emulsion Acid for S. Enhanced Corrosion Resistance of Mild Steel in 1 M HCl Solution by
Simultaneous Acid and Proppant Fracturing. Of fshore Technology Trace Amount of 2-Phenyl-Benzothiazole Derivatives: Experimental,
Conference, SPE-24332-MS, 2013. Quantum Chemical Calculations and Molecular Dynamics (MD)
(8) Li, N.; Dai, J.; Li, J.; Bai, F.; Liu, P.; Luo, Z. Application Status and Simulation Studies. Corros. Sci. 2017, 114, 133−145.
Research Progress of Shale Reservoirs Acid Treatment Technology. (29) ASTM, A. G31-72: Standard Practice for Laboratory Immersion
Natural Gas Industry B 2016, 3 (2), 165−172. Corrosion Testing of Metals, Annual Book of ASTM Standards; American
(9) Williams, B. B.; Gidley, J. L.; Schechter, R. S. Acidizing Society for Testing and Materials: Philadelphia, PA, 2004.
Fundamentals; Henry L. Doherty Memorial Fund of AIME, Society of (30) Williams, J. M. High Internal Phase Water-in-Oil Emulsions:
Petroleum Engineers of AIME, 1979. Influence of Surfactants and Cosurfactants on Emulsion Stability and
(10) Nasr-El-Din, H. A.; Al-Anazi, H. A.; Mohamed, S. K. Stimulation Foam Quality. Langmuir 1991, 7 (7), 1370−1377.
of Water-Disposal Wells Using Acid-in-Diesel Emulsions: Case (31) Boyd, J.; Parkinson, C.; Sherman, P. Factors Affecting Emulsion
Histories. SPE Prod. Facil. 2000, 15 (03), 176−182. Stability, and the HLB Concept. J. Colloid Interface Sci. 1972, 41 (2),
(11) Taylor, K. C.; Nasr-El-Din, H. A. Laboratory Evaluation of In-Situ 359−370.
Gelled Acids for Carbonate Reservoirs. SPE Journal 2003, 8 (04), 426− (32) Aveyard, R.; Binks, B. P.; Mead, J. Interfacial Tension Minima in
434. Oil−water−surfactant Systems. Effects of Alkane Chain Length and
(12) Cairns, A. J.; Al-Muntasheri, G. A.; Sayed, M.; Fu, L.; Giannelis, E. Presence of N-Alkanols in Systems Containing Aerosol OT. J. Chem.
P. Targeting Enhanced Production through Deep Carbonate Soc., Faraday Trans. 1 1986, 82 (6), 1755−1770.
Stimulation: Stabilized Acid Emulsions. SPE International Conference (33) Singh, R.; Mohanty, K. K. Synergy between Nanoparticles and
and Exhibition on Formation Damage Control, SPE-178967, 2016. Surfactants in Stabilizing Foams for Oil Recovery. Energy Fuels 2015, 29,
(13) Kalfayan, L. J. Fracture Acidizing: History, Present State, and 467−479.
Future. SPE Hydraulic Fracturing Technology Conference, SPE-106371- (34) Finšgar, M.; Jackson, J. Application of Corrosion Inhibitors for
MS, 2007. Steels in Acidic Media for the Oil and Gas Industry: A Review. Corros.
(14) Singh, R.; Mohanty, K. K. Foams Stabilized by In-Situ Surface- Sci. 2014, 86, 17−41.
Activated Nanoparticles in Bulk and Porous Media. SPE Journal 2016, (35) Smith, C. F.; Dollarhide, F. E.; Byth, N. J. Acid Corrosion
21 (01), 121−130. Inhibitors - Are We Getting What We Need? JPT, J. Pet. Technol. 1978,
(15) Singh, R.; Mohanty, K. K. Foam Flow in a Layered, 30 (05), 737−746.
Heterogeneous Porous Medium: A Visualization Study. Fuel 2017, (36) Still, J. W.; Dismuke, K.; Frenier, W. W. Generating Acid
197, 58−69. Downhole in Acid Fracturing. Patent US7166560B2, January 23, 2007.
(16) Binks, B. P.; Murakami, R. Phase Inversion of Particle-Stabilized (37) Burgos, G.; Birch, G.; Buijse, M. Acid Fracturing With
Materials from Foams to Dry Water. Nat. Mater. 2006, 5 (11), 865−869. Encapsulated Citric Acid. SPE International Symposium and Exhibition
(17) Dieter, S.; Franz-Theo, S.; Helmut, B. Predominantly Aqueous on Formation Damage Control, SPE-86484-MS, 2004.
Compositions in a Fluffy Powdery Form Approximating Powdered (38) Nasr-El-Din, H. A.; Al-Zahrani, A. A.; Garzon, F. O.; Giraldo, C. A.
Solids Behavior and Process for Forming Same. Patent US3393155A, F.; Al-Hakami, I. M.; Al-Marri, H. M. Acid Fracturing of Gas Wells by
July 16, 1968. Use of an Acid Precursor in the Form of Solid Beads: Lessons Learned
(18) Forny, L.; Saleh, K.; Pezron, I.; Komunjer, L.; Guigon, P. From First Field Application. SPE Production & Operations 2009, 24
Influence of Mixing Characteristics for Water Encapsulation by Self- (02), 320−335.
Assembling Hydrophobic Silica Nanoparticles. Powder Technol. 2009, (39) Mohanty, K. K.; Panthi, K.; Singh, R. Microparticle Carriers for
189 (2), 263−269. Aqueous Compositions and Methods of Making. Patent Application no.
(19) Forny, L.; Saleh, K.; Denoyel, R.; Pezron, I. Contact Angle 62/366,820, filed July 26, 2016.
Assessment of Hydrophobic Silica Nanoparticles Related to the
Mechanisms of Dry Water Formation. Langmuir 2010, 26 (4), 2333−
2338.
(20) Wang, W.; Bray, C. L.; Adams, D. J.; Cooper, A. I. Methane
Storage in Dry Water Gas Hydrates. J. Am. Chem. Soc. 2008, 130 (35),
11608−11609.
(21) Hu, G.; Ye, Y.; Liu, C.; Meng, Q.; Zhang, J.; Diao, S. Direct
Measurement of Formation and Dissociation Rate and Storage Capacity
of Dry Water Methane Hydrates. Fuel Process. Technol. 2011, 92 (8),
1617−1622.
(22) Carter, B. O.; Adams, D. J.; Cooper, A. I. Pausing a Stir:
Heterogeneous Catalysis in “dry Water. Green Chem. 2010, 12 (5), 783−
785.
(23) Sousa, F. L.; Bustamante, R.; Millán, A.; Palacio, F.; Trindade, T.;
Silva, N. J. O. Magnetically Responsive Dry Fluids. Nanoscale 2013, 5
(16), 7229−7233.
(24) Panthi, K.; Singh, R.; Mohanty, K. K. Microencapsulation and
Stimuli-Responsive Controlled Release of Particles Using Water-in-Air
Powders. Langmuir 2017, 33 (16), 3998−4010.

11764 DOI: 10.1021/[Link].7b02003

Energy Fuels 2017, 31, 11755−11764