Publications by Year: 2015

2015
Z. Xue, Worthen, A. J., Da, C., Qajar, A., Ketchum, I. R., Alzobaidi, S., Huh, C., Prodanović, M., and Johnston, K. P., “Ultradry Carbon Dioxide-in-Water Foams with Viscoelastic Aqueous Phases,” Langmuir, vol. 32, no. 1, pp. 28-37, 2015. Publisher's VersionAbstract
For foams with ultra low water contents, the capillary pressure is very large and induces rapid drainage that destabilizes the aqueous lamellae between the gas bubbles. However, we show that high-pressure CO2-in-water foams can be stabilized with a viscoelastic aqueous phase composed of entangled wormlike micelles, even for extremely high CO2 volume fractions ϕ of 0.95 to 0.98; the viscosity of these ultradry foams increased by up to 3–4-fold, reaching more than 100 cP relative to foams formed with conventional low viscosity aqueous phases. The foam morphology consisted of fine ∼20 μm polyhedral-shaped CO2 bubbles that were stable for hours. The wormlike micelles were formed by mixing anionic sodium lauryl ether sulfate (SLES) with salt and a protonated cationic surfactant, as shown by cryogenic transmission electron microscopy (cryo-TEM) and large values of the zero-shear viscosity and the dynamic storage and loss moduli. With the highly viscous continuous aqueous phases, the foam lamella drainage rates were low, as corroborated by confocal microscopy. The preservation of viscous thick lamellae resulted in lower rates of Ostwald ripening relative to conventional foams as shown by high-pressure optical microscopy. The ability to stabilize viscous ultra high internal phase foams is expected to find utility in various practical applications, including nearly “waterless” fracturing fluids for recovery of oil and gas in shale, offering the possibility of a massive reduction in the amount of wastewater
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.
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.
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.
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.
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.
K. Y. Yoon, Mehrmohammadi, M., Borwankar, A., Emelianov, S. Y., and Johnston, K. P., “Synthesis of Iron Oxide Nanoclusters with Enhanced Magnetization and Their Applications in Pulsed Magneto-Motive Ultrasound Imaging,” Nano, vol. 10, no. 05, pp. 1550073, 2015. Publisher's VersionAbstract
We report here a facile synthetic approach for preparing water-soluble Fe3O4 nanoparticle (NP) clusters with tunable size distribution and magnetic properties. The primary NP sizes were controlled by tuning the nucleation and growth rates with temperature and ligand concentration while the nanocluster sizes were manipulated by controlling interparticle interactions. We have investigated the size control of clusters as well as individual primary NPs via dynamic light scattering (DLS) analysis and transmission electron microscopy (TEM). Superconducting quantum interference device (SQUID) was used to measure the magnetic properties of Fe3O4 NP for determining the effect of size distribution at room temperature. These water dispersible NP clusters can be utilized in various biomedical applications. In this study, we demonstrated the application of synthesized nanoclusters to enhance imaging contrast a novel ultrasound-based imaging modality, pulsed magneto-motive ultrasound (pMMUS) imaging. Our results indicated that by using the NP clusters with enhanced magnetic properties, the pMMUS signal increased significantly which is an essential requirement for further development of in vivo pMMUS imaging.Read More: http://www.worldscientific.com/doi/abs/10.1142/S1793292015500733
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, 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.
R. B. Jadrich, Bollinger, J. A., Johnston, K. P., and Truskett, T. M., “Origin and detection of microstructural clustering in fluids with spatial-range competitive interactions,” Physical Review E, vol. 91, no. 4, pp. 042312, 2015. Publisher's VersionAbstract
Fluids with competing short-range attractions and long-range repulsions mimic dispersions of charge-stabilized colloids that can display equilibrium structures with intermediate-range order (IRO), including particle clusters. Using simulations and analytical theory, we demonstrate how to detect cluster formation in such systems from the static structure factor and elucidate links to macrophase separation in purely attractive reference fluids. We find that clusters emerge when the thermal correlation length encoded in the IRO peak of the structure factor exceeds the characteristic length scale of interparticle repulsions. We also identify qualitative differences between the dynamics of systems that form amorphous versus microcrystalline clusters.
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.
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
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.
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.
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. 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.
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.
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.