Publications

2016
C. Da, Xue, Z., Worthen, A. J., Qajar, A., Huh, C., Prodanovic, M., and Johnston, K. P., “Viscosity and stability of dry CO 2 foams for improved oil recovery,” SPE Improved Oil Recovery Conference. Society of Petroleum Engineers, 2016. Publisher's VersionAbstract
CO2/water foams are of interest for mobility control in CO2 EOR and as energized fracture fluids, or hybrid processes that combine aspects of both processes. In fracturing applications, it would be desirable to lower the water level as much as possible to minimize the production of wastewater and formation damage. It is challenging to stabilize ultra dry foams with extremely high internal phase gas fraction given the high capillary pressure and the rapid drainage rate of the lamellae between the gas bubbles. However, we demonstrate that these ultra dry CO2-in-water foams may be stabilized with surfactants that form viscoelastic wormlike micelles in the aqueous phase. These wormlike micelles are formed by tuning the surfactant packing parameter with electrolytes or a second oppositely-charged surfactant to stabilize ultradry CO2-in-water foams with foam qualities as high as 0.98 and apparent viscosities more than 100 cP up to 90 °C. Applicability of these foams for improved oil recovery is evaluated by running multiphase flow injection simulations in a case-study oil reservoir.
Z. Xue, Worthen, A., Qajar, A., Robert, I., Bryant, S. L., Huh, C., Prodanović, M., and Johnston, K. P., “Viscosity and stability of ultra-high internal phase CO 2-in-water foams stabilized with surfactants and nanoparticles with or without polyelectrolytes,” Journal of colloid and interface science, vol. 461, pp. 383-395, 2016. Publisher's VersionAbstract
To date, relatively few examples of ultra-high internal phase supercritical CO2-in-water foams (also referred to as macroemulsions) have been observed, despite interest in applications including “waterless” hydraulic fracturing in energy production. The viscosities and stabilities of foams up to 0.98 CO2 volume fraction were investigated in terms of foam bubble size, interfacial tension, and bulk and surface viscosity. The foams were stabilized with laurylamidopropyl betaine (LAPB) surfactant and silica nanoparticles (NPs), with and without partially hydrolyzed polyacrylamide (HPAM). For foams stabilized with mixture of LAPB and NPs, fine ∼70 μm bubbles and high viscosities on the order of 100 cP at >0.90 internal phase fraction were stabilized for hours to days. The surfactant reduces interfacial tension, and thus facilitates bubble generation and decreases the capillary pressure to reduce the drainage rate of the lamella. The LAPB, which is in the cationic protonated form, also attracts anionic NPs (and anionic HPAM in systems containing polymer) to the interface. The adsorbed NPs at the interface are shown to slow down Ostwald ripening (with or without polymer added) and increase foam stability. In systems with added HPAM, the increase in the bulk and surface viscosity of the aqueous phase further decreases the lamella drainage rate and inhibits coalescence of foams. Thus, the added polymer increases the foam viscosity by threefold. Scaling law analysis shows the viscosity of 0.90 volume fraction foams is inversely proportional to the bubble size. Graphical abstract
A. U. Borwankar, Dear, B. J., Twu, A., Hung, J. J., Dinin, A. K., Wilson, B. K., Yue, J., Maynard, J. A., Truskett, T. M., and Johnston, K. P., “Viscosity reduction of a concentrated monoclonal antibody with arginine· HCl and arginine· glutamate,” Industrial & Engineering Chemistry Research, vol. 55, no. 43, pp. 11225-11234, 2016. Publisher's VersionAbstract
To further advance a subcutaneous injection of monoclonal antibodies (mAbs) at elevated concentrations, novel concepts are needed to lower the viscosity. The addition of high concentrations of cosolutes, namely, arginine glutamate (Arg·Glu) or Arg·HCl, reduced the viscosity of a ∼250 mg/mL mAb solution up to 6-fold. With Arg·Glu, the viscosity of the mAb solution was reduced to 30 cP and for a polyclonal sheep IgG solution to 17 cP both at ∼250 mg/mL. Viscosities went through a maximum at the mAb isoelectric point for solutions with Arg·Glu or Arg·HCl. In contrast the viscosity was only weakly affected by NaCl or the preferentially excluded molecule trehalose. The large viscosity reduction from Arg may be attributed to direct binding to the mAb, resulting in suppression of both hydrophobic and local anisotropic electrostatic attraction. Aggregate formation was negligible for high cosolute mAb solutions as demonstrated by SEC even after 8 weeks of 25 °C storage
T. J. Mefford, Rong, X., Abakumov, A. M., Hardin, W. G., Dai, S., Kolpak, A. M., Johnston, K. P., and Stevenson, K. J., “Water electrolysis on La1-xSrxCoO3-[delta] perovskite electrocatalysts,” Nature communications, vol. 7, 2016. Publisher's VersionAbstract
Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1−xSrxCoO3−δ. We attempt to rationalize the high activities of La1−xSrxCoO3−δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.
2015
Q. Nguyen, Hirasaki, G., and Johnston, K., “Novel CO2 Foam Concepts and Injection Schemes for Improving CO2 Sweep Efficiency in Sandstone and Carbonate Hydrocarbon Formations,” Univ. of Texas, Austin, TX (United States), 2015. Publisher's VersionAbstract
We explored cationic, nonionic and zwitterionic surfactants to identify candidates that have the potential to satisfy all the key requirements for CO2 foams in EOR. We have examined the formation, texture, rheology and stability of CO2 foams as a function of the surfactant structure and formulation variables including temperature, pressure, water/CO2 ratio, surfactant concentration, salinity and concentration of oil. Furthermore, the partitioning of surfactants between oil and water as well as CO2 and water was examined in conjunction with adsorption measurements on limestone by the Hirasaki lab to develop strategies to optimize the transport of surfactants in reservoirs
D. DiCarlo, Huh, C., and Johnston, K. P., “Area 2: Use Of Engineered Nanoparticle-Stabilized CO2 Foams To Improve Volumetric Sweep Of CO2 EOR Processes,” National Energy Technology Laboratory (NETL), 2015. Publisher's VersionAbstract
The goal of this project was to develop a new CO2 injection enhanced oil recovery (CO2- EOR) process using engineered nanoparticles with optimized surface coatings that has better volumetric sweep efficiency and a wider application range than conventional CO2-EOR processes. The main objectives of this project were to (1) identify the characteristics of the optimal nanoparticles that generate extremely stable CO2 foams in situ in reservoir regions without oil; (2) develop a novel method of mobility control using “self-guiding” foams with smart nanoparticles; and (3) extend the applicability of the new method to reservoirs having a wide range of salinity, temperatures, and heterogeneity. Concurrent with our experimental effort to understand the foam generation and transport processes and foam-induced mobility reduction, we also developed mathematical models to explain the underlying processes and mechanisms that govern the fate of nanoparticle-stabilized CO2 foams in porous media and applied these models to (1) simulate the results of foam generation and transport experiments conducted in beadpack and sandstone core systems, (2) analyze CO2 injection data received from a field operator, and (3) aid with the design of a foam injection pilot test. Our simulator is applicable to near-injection well field-scale foam injection problems and accounts for the effects due to layered heterogeneity in permeability field, foam stabilizing agents effects, oil presence, and shear-thinning on the generation and transport of nanoparticle-stabilized C/W foams. This report presents the details of our experimental and numerical modeling work and outlines the highlights of our findings
K. Sokolov, Stover, R., Joshi, P., Yoon, S. J., Murthy, A., Emelianov, S., and Johnston, K., “Biodegradable Plasmonic Nanoparticles: Overcoming Clinical Translation Barriers,” Optical Molecular Probes, Imaging and Drug Delivery. Optical Society of America, pp. OM3D. 4, 2015. Publisher's VersionAbstract
We present biodegradable gold nanoparticles with plasmon resonances in the NIR region that can provide a crucial link between the enormous potential of metal nanoparticles for cancer imaging and therapy and translation into clinical practice.
Y. Chen, Elhag, A. S., Cui, L., Worthen, A. J., Reddy, P. P., Noguera, J. A., Ou, A. M., Ma, K., Puerto, M., and Hirasaki, G. J., “CO2-in-water foam at elevated temperature and salinity stabilized with a nonionic surfactant with a high degree of ethoxylation,” Industrial & Engineering Chemistry Research, vol. 54, no. 16, pp. 4252-4263, 2015. Publisher's VersionAbstract
The utilization of nonionic surfactants for stabilization of CO2 foams has been limited by low aqueous solubilities at elevated temperatures and salinities. In this work, a nonionic surfactant C12–14(EO)22 with a high degree of ethoxylation resulted in a high cloud point temperature of 83 °C even in 90 g/L NaCl brine. Despite the relatively high hydrophilic–CO2-philic balance, the surfactant adsorption at the C–W interface lowered the interfacial tension to ∼7 mN/m at a CO2density of ∼0.85 g/mL, as determined with captive bubble tensiometry. The adsorption was sufficient to stabilize a CO2-in-water (C/W) foam with an apparent viscosity of ∼7 cP at 80 °C, essentially up to the cloud point temperature, in the presence of 90 g/L NaCl brine in a 30 darcy sand pack. In a 1.2 darcy glass bead pack, the apparent viscosity of the foam in the presence of 0.8% total dissolved solids (TDS) brine reached the highest viscosity of ∼350 cP at 60% foam quality (volume percent CO2) at a low superficial velocity of 6 ft/day. Shear-thinning behavior was observed in both the glass bead pack and the sand pack irrespective of the permeability difference. In addition, C12–14(EO)22 stabilized C/W foam with an apparent viscosity of 80–100 cP in a 49 mdarcy dolomite core formed through a coinjection and a surfactant-alternating-gas process. The dodecane–0.8% TDS brine partition coefficient for C12–14(EO)22 was below 0.1 at 40 °C and 1 atm. The formation of strong foam in the porous media and the low oil–brine partition coefficient indicate C12–14(EO)22 has potential for CO2-enhanced oil recovery.
Z. Xue, Panthi, K., Fei, Y., Johnston, K. P., and Mohanty, K. K., “CO2-Soluble Ionic Surfactants and CO2 Foams for High-Temperature and High-Salinity Sandstone Reservoirs,” Energy & Fuels, vol. 29, no. 9, pp. 5750-5760, 2015. Publisher's VersionAbstract
The sweep efficiency of CO2 enhanced oil recovery can be improved by forming viscous CO2-in-water (C/W) foams that increase the viscosity of CO2. The goal of this study is to identify CO2-soluble ionic surfactants that stabilize C/W foams at elevated temperatures up to 120 °C in the presence of a high salinity brine using aqueous phase stability, static and dynamic adsorption, CO2 solubility, interfacial tension, foam bubble size, and foam viscosity measurements. An anionic sulfonate surfactant and an amphoteric acetate surfactant were selected to achieve good thermal and chemical stability, and to minimize adsorption to sandstone reservoirs in the harsh high-salinity high-temperature brine. The strong solvation of the surfactant head by the brine phase and surfactant tail by CO2 allows efficient reduction of the C/W interfacial tension, and the formation of viscous C/W foams at high salinity and high temperature. Furthermore, the effect of temperature and methane dilution of CO2 on foam viscosity was evaluated systematically in both bulk and porous media. High temperature reduces the stability of foam lamella, which leads to lower lamella density and, therefore, lower foam viscosity. Methane dilution of CO2 reduces the solvation of surfactant tails and makes the surfactant less CO2-philic at the interface. The consequent increase of the interfacial tension decreases the stability of foam lamella, as seen by the increase in foam bubble size, thereby reducing foam viscosity.
A. W. Sanders, Johnston, K. P., Nguyen, Q., Adkins, S., Chen, X., and Rightor, E. G., “Compositions for oil recovery and methods of their use”. US Patent 8,973,668, 2015. Publisher's VersionAbstract
Embodiments of the present disclosure include compositions for use in enhanced oil recovery, and methods of using the compositions for recovering oil. Compositions of the present disclosure include a nonionic, non-emulsifying surfactant having a CO2-philicity in a range of about 1.5 to about 5.0, carbon dioxide in a liquid phase or supercritical phase, and water, where the nonionic, non-emulsifying surfactant promotes a formation of a stable foam formed of carbon dioxide and water
C. Huh, Bryant, S. L., Milner, T. E., and Johnston, K. P., “Determination of oil saturation in reservoir rock using paramagnetic nanoparticles and magnetic field”. US Patent App. 14/853,519, 2015. Publisher's VersionAbstract
Methods for detection of the presence and distribution of oil in subsurface formation are described herein. The present invention involves injection of an aqueous dispersion of the nanoparticles into the potentially oil containing subsurface formation, followed by a remote detection of the oscillation responses of the nanoparticles in the oil/water interfaces in the reservoir rock by applying magnetic field.
C. Huh, Bryant, S. L., Milner, T. E., and Johnston, K. P., “Determination of oil saturation in reservoir rock using paramagnetic nanoparticles and magnetic field”. US Patent 9,133,709, 2015. Publisher's VersionAbstract
Methods for detection of the presence and distribution of oil in subsurface formation are described herein. The present invention involves injection of an aqueous dispersion of the nanoparticles into the potentially oil containing subsurface formation, followed by a remote detection of the oscillation responses of the nanoparticles in the oil/water interfaces in the reservoir rock by applying magnetic field.
J. E. Hitt, Rogers, T. L., Gillespie, I. B., Scherzer, B. D., Garcia, P. C., Beck, N. S., Tucker, C. J., Young, T. J., Hayes, D. A., and Williams III, R. O., “Enhanced delivery of drug compositions to treat life threatening infections”. US Patent 9,061,027, 2015. Publisher's VersionAbstract
Inhalable compositions are described. The inhalable compositions comprise one or more respirable aggregates, the respirable aggregates comprising one or more poorly water soluble active agents, wherein at least one of the active agents reaches a maximum lung concentration (Cmax) of at least about 0.25 μg/gram of lung tissue and remains at such concentration for a period of at least one hour after being delivered to the lung. Methods for making such compositions and methods for using such compositions are also disclosed.
R. O. Williams III, Johnston, K. P., Sinswat, P., McConville, J. T., Talbert, R., Peters, J. I., Watts, A. B., and Rogers, T. L., “Enhanced delivery of immunosuppressive drug compositions for pulmonary delivery”. US Patent App. 14/621,337, 2015. Publisher's VersionAbstract
The present invention includes compositions and methods for making and using a rapid dissolving, high potency, substantially amorphous nanostructured aggregate for pulmonary delivery of tacrolimus and a stabilizer matrix comprising, optionally, a polymeric or non-polymeric surfactant, a polymeric or non-polymeric saccharide or both, wherein the aggregate comprises a surface area greater than 5 m2/g as measured by BET analysis and exhibiting supersaturation for at least 0.5 hours when 11-15-times the aqueous crystalline solubility of tacrolimus is added to simulated lung fluid.
R. O. Williams, Johnston, K. P., Sinswat, P., McConville, J. T., Talbert, R., Peters, J. I., Watts, A. B., and Rogers, T. L., “Enhanced delivery of immunosuppressive drug compositions for pulmonary delivery”. US Patent 9,044,391, 2015. Publisher's VersionAbstract
The present invention includes compositions and methods for making and using a rapid dissolving, high potency, substantially amorphous nanostructured aggregate for pulmonary delivery of tacrolimus and a stabilizer matrix comprising, optionally, a polymeric or non-polymeric surfactant, a polymeric or non-polymeric saccharide or both, wherein the aggregate comprises a surface area greater than 5 m2/g as measured by BET analysis and exhibiting supersaturation for at least 0.5 hours when 11-15-times the aqueous crystalline solubility of tacrolimus is added to simulated lung fluid.
K. P. Johnston, Engstrom, J., and Williams III, R. O., “Formation of stable submicron peptide or protein particles by thin film freezing”. US Patent 8,968,786, 2015. Publisher's VersionAbstract
The present invention includes compositions and methods for preparing micron-sized or submicron-sized particles by dissolving a water soluble effective ingredient in one or more solvents; spraying or dripping droplets solvent such that the effective ingredient is exposed to a vapor-liquid interface of less than 50, 100, 150, 200, 250, 200, 400 or 500 cm−1 area/volume to, e.g., increase protein stability; and contacting the droplet with a freezing surface that has a temperature differential of at least 30° C. between the droplet and the surface, wherein the surface freezes the droplet into a thin film with a thickness of less than 500 micrometers and a surface area to volume between 25 to 500 cm−1.
K. P. Johnston, Engstrom, J., and Williams III, R. O., “Formation of stable submicron peptide or protein particles by thin film freezing”. US Patent App. 14/603,211, 2015. Publisher's VersionAbstract
The present invention includes compositions and methods for preparing micron-sized or submicron-sized particles by dissolving a water soluble effective ingredient in one or more solvents; spraying or dripping droplets solvent such that the effective ingredient is exposed to a vapor-liquid interface of less than 50, 100, 150, 200, 250, 200, 400 or 500 cm−1 area/volume to, e.g., increase protein stability; and contacting the droplet with a freezing surface that has a temperature differential of at least 30° C. between the droplet and the surface, wherein the surface freezes the droplet into a thin film with a thickness of less than 500 micrometers and a surface area to volume between 25 to 500 cm−1.
A. U. Borwankar, Willsey, B. W., Twu, A., Hung, J. J., Stover, R. J., Wang, T. W., Feldman, M. D., Milner, T. E., Truskett, T. M., and Johnston, K. P., “Gold nanoparticles with high densities of small protuberances on nanocluster cores with strong NIR extinction,” RSC Advances, vol. 5, no. 127, pp. 104674-104687, 2015. Publisher's VersionAbstract
Plasmonic nanoparticles with sizes well below 100 nm and high near infrared (NIR) extinction are of great interest in biomedical imaging. Herein we present ∼60 nm Au nanoparticles with high NIR absorbance at wavelengths ranging from 700 nm to 1100 nm, which were synthesized under kinetic control. A high surface density of protuberances is grown on ∼30 nm nanocluster cores, which are composed of ∼10 nm primary particles. The high NIR extinction is produced by a combination of the close proximity of the primary particles in the cores, the high surface density of protuberances, and the high aspect ratio of the length of the protuberances to the diameter of the primary particles. When the Au precursor was reduced more slowly at a higher pH of 9.3, the growth was thermodynamically controlled and the nanocluster cores relaxed to spheres. This concept of self-assembly during reaction to change the morphology of nanoclusters and decorated nanoclusters, may be expected to be applicable to a wide variety of systems by balancing kinetic and thermodynamic control, along with the colloidal interactions.
K. P. Johnston, Truskett, T., Dear, B., Dinin, A., Borwankar, A., and Hung, J., “Low viscosity concentrated protein dispersions”. US Patent App. 14/843,897, 2015. Publisher's VersionAbstract
Disclosed herein are, inter alia, low viscosity dispersions comprising proteins and viscosity lowering agents; pharmaceutical compositions comprising low viscosity dispersions; and methods of making and using the pharmaceutical compositions and low viscosity dispersions.
A. Worthen, Taghavy, A., Aroonsri, A., Kim, I., Johnston, K., Huh, C., Bryant, S., and DiCarlo, D., “Multi-Scale Evaluation of Nanoparticle-Stabilized CO 2-in-Water Foams: From the Benchtop to the Field,” SPE Annual Technical Conference and Exhibition. Society of Petroleum Engineers, 2015. Publisher's VersionAbstract
Although EOR with CO2 is practiced domestically on large scale, the potential for advancement is enormous. The ongoing search for better solutions has motivated extensive research on alternatives to surfactant-stabilized CO2 foams for CO2 mobility control. The formation of CO2-in-water foams lowers the CO2 mobility, resulting in improvement in sweep efficiency in field tests. The crucial unmet challenge in employing CO2 foams is to maintain long-term stability of foam to achieve high sweep efficiency for the duration of the flooding process. Surfactant-stabilized foams are inherently unstable so that maintenance of the low mobility requires continuous regeneration of lamellae in the small pores of the rock. Nanoparticles can potentially be used to provide much higher foam stability and thus long-term mobility control for CO2 floods. They can act like a foaming surfactant without some of the surfactant drawbacks. Here we present a turnkey approach for using surface treated nanoparticles in reservoirs. This involves: tests for stability in brines, transportability through cores, foam generation in beadpacks and cores when co-injected with CO2, quantification of CO2 viscosity enhancement, and finally modeling of field-scale effects. In this paper, we will outline the key details of nanoparticle design for CO2 EOR.

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