Publications

2017
B. J. Dear, Hung, J. J., Truskett, T. M., and Johnston, K. P., “Contrasting the Influence of Cationic Amino Acids on the Viscosity and Stability of a Highly Concentrated Monoclonal Antibody,” Pharmaceutical Research, vol. 34, no. 1, pp. 193-207, 2017. Publisher's VersionAbstract
Purpose To explain the effects of cationic amino acids and other co-solutes on the viscosity, stability and protein-protein interactions (PPI) of highly concentrated (≥200 mg/ml) monoclonal antibody (mAb) solutions to advance subcutaneous injection. Methods The viscosities of ≥200 mg/ml mAb1 solutions with various co-solutes and pH were measured by capillary rheometry in some cases up to 70,000 s−1. The viscosities are analyzed in terms of dilute PPI characterized by diffusion interaction parameters (kD) from dynamic light scattering (DLS). MAb stability was measured by turbidity and size exclusion chromatography (SEC) after 4 weeks of 40°C storage. Results Viscosity reductions were achieved by reducing the pH, or adding histidine, arginine, imidazole or camphorsulfonic acid, each of which contains a hydrophobic moiety. The addition of inorganic electrolytes or neutral osmolytes only weakly affected viscosity. Systems with reduced viscosities also tended to be Newtonian, while more viscous systems were shear thinning. Conclusions Viscosity reduction down to 20 cP at 220 mg/ml mAb1 was achieved with co-solutes that are both charged and contain a hydrophobic interaction domain for sufficient binding to the protein surface. These reductions are related to the DLS diffusion interaction parameter, kD, only after normalization to remove the effect of charge screening. Shear rate profiles demonstrate that select co-solutes reduce protein network formation.
M. Iqbal, Lyon, B. A., Ureña-Benavides, E. E., Moaseri, E., Fei, Y., McFadden, C., Javier, K. J., Ellison, C. J., Pennell, K. D., and Johnston, K. P., “High temperature stability and low adsorption of sub 100 nm magnetite nanoparticles grafted with sulfonated copolymers on Berea sandstone in high salinity brine,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, vol. 520, pp. 257-267, 2017. Publisher's VersionAbstract
The synthesis of polymer grafted nanoparticles that are stable at high salinities and high temperature with low retention in porous media is of paramount importance for subsurface applications including electromagnetic imaging, enhanced oil recovery and environmental remediation. Herein, we present an improved approach to synthesize and purify sub-100 nm IONPs grafted with a random copolymer poly(AMPS-co-AA) (poly(2-acrylamido-3-methylpropanesulfonate-co-acrylic acid)) by means of catalyzed amide bond formation at room temperature. The improved and uniform polymer grafting of magnetic nanoparticles led to colloidal stability of IONPs at high temperature (120 °C) in API for a month. The transport behavior of the polymer grafted IONPs was investigated in crushed and in consolidated Berea sandstone. The high poly (AMPS-co-AA) polymer level on the surface (∼34%) provided electrosteric stabilization between the NPs and weak interactions of the NPs with anionic silica and sandstone surfaces. This behavior was enabled by low affinity of Ca2+ towards the highly acidic AMPS monomers thus enabling strong solvation in API brine. In crushed Berea sandstone, the retention was reduced by three fold and nine fold relative to our earlier studies, given the improvements in the grafted polymer layer. For intact core flood experiments in Berea sandstone carried out at elevated temperature (65 °C) and pressure (1000 psi net confining stress), the retention was 519 μg/g, comparable to the value for crushed Berea sandstone. Furthermore, the addition of a relatively small amount (0.1% v/v) of commercially available sacrificial polymer (e.g., HEC-10) further reduced IONP retention to 252 μg/g or 0.17 mg/m2 by blocking retentive sites
S. Alzobaidi, Da, C., Tran, V., Prodanović, M., and Johnston, K. P., “High temperature ultralow water content carbon dioxide-in-water foam stabilized with viscoelastic zwitterionic surfactants,” Journal of Colloid and Interface Science, vol. 488, pp. 79-91, 2017. Publisher's VersionAbstract
Ultralow water content carbon dioxide-in-water (C/W) foams with gas phase volume fractions (ϕ) above 0.95 (that is <0.05 water) tend to be inherently unstable given that the large capillary pressures that cause the lamellar films to thin. Herein, we demonstrate that these C/W foams may be stabilized with viscoelastic aqueous phases formed with a single zwitterionic surfactant at a concentration of only 1% (w/v) in DI water and over a wide range of salinity. Moreover, they are stable with a foam quality ϕ up to 0.98 even for temperatures up to 120 °C. The properties of aqueous viscoelastic solutions and foams containing these solutions are examined for a series of zwitterionic amidopropylcarbobetaines, R-ONHC3H6N(CH3)2CH2CO2, where R is varied from C12–14 (coco) to C18 (oleyl) to C22 (erucyl). For the surfactants with long C18 and C22 tails, the relaxation times from complex rheology indicate the presence of viscoelastic wormlike micelles over a wide range in salinity and pH, given the high surfactant packing fraction. The apparent viscosities of these ultralow water content foams reached more than 120 cP with stabilities more than 30-fold over those for foams formed with the non-viscoelastic C12–14 surfactant. At 90 °C, the foam morphology was composed of ∼35 μm diameter bubbles with a polyhedral texture. The apparent foam viscosity typically increased with ϕ and then dropped at ϕ values higher than 0.95–0.98. The Ostwald ripening rate was slower for foams with viscoelastic versus non-viscoelastic lamellae as shown by optical microscopy, as a consequence of slower lamellar drainage rates. The ability to achieve high stabilities for ultralow water content C/W foams over a wide temperature range is of interest in various technologies including polymer and materials science, CO2 enhanced oil recovery, CO2 sequestration (by greater control of the CO2flow patterns), and possibly even hydraulic fracturing with minimal use of water to reduce the requirements for wastewater disposal.
2016
K. Y. Yoon, Xue, Z., Fei, Y., Lee, J., Cheng, V., Bagaria, H. G., Huh, C., Bryant, S. L., Kong, S. D., and Ngo, V. W., “Control of magnetite primary particle size in aqueous dispersions of nanoclusters for high magnetic susceptibilities,” Journal of colloid and interface science, vol. 462, pp. 359-367, 2016. Publisher's VersionAbstract
Aqueous dispersions of iron oxide nanoparticles with a high initial magnetic susceptibility (χi) are of interest as contrast agents in electromagnetic tomography. Nanoclusters composed of iron oxide primary particles were formed by co-precipitation of Fe(II) and Fe(III) chlorides at alkaline conditions and high temperature of 95 °C. Two-step addition of citrate was used to produce large primary particles and then stabilize the nanoclusters. The size of the primary particles was tuned from 5 nm to 15 nm by varying the citrate/iron precursor ratio during the normal phase hydrolysis reaction, while the second iteration of citrate stabilized the nanoclusters with hydrodynamic diameters of 30–75 nm. The crystallinity of the iron oxide nanoparticles was promoted by annealing at 95 °C and systematically studied with Superconducting Quantum Interference Device (SQUID), Vibrating Sample Magnetometer (VSM), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). The dependence of χi was examined over a range of low volume fractions (0.005 < θ < 0.02) to understand the magnetic behavior of dispersions. The χi of the dispersions increased markedly with the size and concentration of the constituent primary particles, reaching an unusually high value of 0.85 at 1.6% v/v for 15 nm primary particles, which is 2–3 times higher than that for typical commercial ferrofluids. The high χi values are favored by the high crystallinity and the large magnetic diameter of 9.3 nm, indicating a relatively thin surface nonmagnetic layer where the spin orientations are disordered. Graphical abstract
M. Lotfollahi, Kim, I., Beygi, M. R., Worthen, A. J., Huh, C., Johnston, K. P., Wheeler, M. F., and DiCarlo, D. A., “Experimental Studies and Modeling of Foam Hysteresis in Porous Media,” SPE Improved Oil Recovery Conference. Society of Petroleum Engineers, 2016. Publisher's VersionAbstract
The use of foam in gas enhanced oil recovery (EOR) processes has the potential to improve oil recovery by reducing gas mobility. Nanoparticles are a promising alternative to surfactants in creating foam in the harsh environments found in many oil fields. We conducted several CO2-in-brine foam generation experiments in Boise sandstones with surface-treated silica nanoparticle in high-salinity conditions. All the experiments were conducted at the fixed CO2 volume fraction (g = 0.75) and fixed flow rate which changed in steps. We started at low flow rates, increased to a medium flow rates followed by decreasing and then increasing into high flow rates. The steady-state foam apparent viscosity was measured as a function of injection velocity. The foam flowing through the cores showed higher foam generation and consequently higher apparent viscosity as the flow rate increased from low to medium and high velocities. At very high velocities, once foam bubbles were finely textured, the foam apparent viscosity was governed by foam shear-thinning rheology rather than foam creation. A noticeable "hysteresis" occurred when the flow velocity was initially increased and then decreased, implying multiple (coarse and strong) foam states at the same superficial velocity. A normalized generation function was combined with CMG-STARS foam model to cover the full spectrum of foam flow behavior observed during the experiments. The new foam model successfully captures foam generation and hysteresis trends observed in presented experiments in this study and other foam generation experiments at different operational conditions (e.g. fixed pressure drop at fixed foam quality, and fixed pressure drop at fixed water velocity) from the literature. The results indicate once foam is generated in porous media, it is possible to maintain strong foam at low injection rates. This makes foam more feasible in field applications where foam generation is limited by high injection rates (or high pressure gradient) that may only exist near the injection well. Therefore, understanding of foam generation, and foam hysteresis in porous media and accurate modeling of the process are necessary steps for efficient foam design in field.
M. Lotfollahi, Kim, I., Beygi, M. R., Worthen, A. J., Huh, C., Johnston, K. P., Wheeler, M. F., and DiCarlo, D. A., “Foam Generation Hysteresis in Porous Media: Experiments and New Insights,” Transport in Porous Media, pp. 1-17, 2016. Publisher's VersionAbstract
Foam application in subsurface processes including environmental remediation, geological carbon-sequestration, and gas-injection enhanced oil recovery (EOR) has the potential to enhance contamination remediation, secure CO2">CO2CO2 storage, and improve oil recovery, respectively. Nanoparticles are a promising alternative to surfactants in creating foam in harsh environments. We conducted CO2">CO2CO2-in-brine foam generation experiments in Boise sandstones with surface-treated silica nanoparticle in high-salinity conditions. All the experiments were conducted at the fixed CO2">CO2CO2 volume fraction and fixed flow rate which changed in steps. The steady-state foam apparent viscosity was measured as a function of injection velocity. The foam flowing through the cores showed higher apparent viscosity as the flow rate increased from low to medium and high velocities. At very high velocities, once foam bubbles were finely textured, the foam apparent viscosity was governed by foam rheology rather than foam creation. A noticeable hysteresis occurred when the flow velocity was initially increased and then decreased, implying multiple (coarse and strong) foam states at the same superficial velocity. A normalized generation function was combined with CMG-STARS foam model to cover full spectrum of foam behavior in the experiments. The new model successfully captures foam generation and hysteresis trends in presented experiments in this study and data from the literature. The results indicate once foam is generated in porous media, it is possible to maintain strong foam at low injection rates. This makes foam more feasible in field applications where foam generation is limited by high injection rates that may only exist near the injection well.
R. J. Stover, Moaseri, E., Gourisankar, S. P., Iqbal, M., Rahbar, N. K., Changalvaie, B., Truskett, T. M., and Johnston, K. P., “Formation of Small Gold Nanoparticle Chains with High NIR Extinction through Bridging with Calcium Ions,” Langmuir, vol. 32, no. 4, pp. 1127-1138, 2016. Publisher's VersionAbstract
The self-assembly of citrate-capped Au nanoparticles (5 nm) resulted in branched nanochains by adding CaCl2 versus spherical nanoclusters for NaCl. These assemblies were formed between 1 s to 30 min by tuning the electrostatic repulsion and the interparticle bridging attraction between the cations and citrate ligands as a function of electrolyte concentration. For dilute Ca2+, strong interparticle bridging favored particle attachment at chain ends. This resulted in the formation of small, branched chains with lengths as short as 20 nm, due to the large Debye length for the diffuse counterions. Furthermore, the bridging produced very small interparticle spacings and sintering, as evident in high-resolution TEM despite the low temperature. This morphology produced a large red shift in the surface plasmon resonance, as characterized by a broad extinction peak with NIR absorption out to 1000 nm, which is unusual for such small particles. Whereas these properties were seen for primary particles with partial citrate monolayers, the degrees of sintering and NIR extinction were small in the case of citrate multilayers. The ability to design the size and shape of nanoparticle clusters as well as the interparticle spacing by tuning bridging and electrostatic interactions may be expected to be quite general and of broad applicability in materials synthesis
J. J. Hung, Borwankar, A. U., Dear, B. J., Truskett, T. M., and Johnston, K. P., “High concentration tangential flow ultrafiltration of stable monoclonal antibody solutions with low viscosities,” Journal of Membrane Science, vol. 508, pp. 113-126, 2016. Publisher's VersionAbstract
During production of concentrated monoclonal antibody formulations by tangential flow ultrafiltration (TFF), high viscosities and aggregation often cause extensive membrane fouling, flux decay and low product yields. To address these challenges, the co-solutes histidine or imidazole were added at high concentrations from 250 to 320 mM to reduce the viscosity by up to ten-fold relative to conventional low co-solute formulations, to as low as 40 cP at 250 mg/mL. At high mAb concentrations of up to 280 mg/mL, the transmembrane flux was increased threefold by adding high concentrations of co-solutes that also lowered the viscosity. Furthermore, the co-solutes also increased the mAb gel point concentration cg by up to 100 mg/mL mAb and thus enhanced concentration polarization-driven back-diffusion of the mAb at the membrane wall, which led to increased fluxes. The low viscosity and hollow fiber filter modules with straight flow paths enabled more uniform TMP and wall shear stress τw profiles, which mitigated the reversible flux decay that results from an axial decline in the local TMP. The concentrated mAb was stable by SEC before and after extended storage at 4 °C and 37 °C.
Y. Chen, Elhag, A. S., Worthen, A. J., Reddy, P. P., Ou, A. M., Hirasaki, G. J., Nguyen, Q. P., Biswal, S. L., and Johnston, K. P., “High Temperature CO2-in-Water Foams Stabilized with Cationic Quaternary Ammonium Surfactants,” Journal of Chemical & Engineering Data, vol. 61, no. 8, pp. 2761-2770, 2016. Publisher's VersionAbstract
The design of surfactants for stabilizing CO2-in-water (brine) (C/W) foams at high temperature is challenging given the low density (solvent strength) of CO2, limited surfactant solubility in brine, and a lack of knowledge of the interfacial and rheological properties. Herein, the tail length of trimethylammonium cationic surfactants was optimized to provide the desired phase behavior and interfacial properties for formation and stabilization of the C/W foams. The headgroup was properly balanced with a C12–14 hydrocarbon tail to achieve aqueous solubility in 22% total dissolved solids (TDS) brine up to 393 K (120 °C) along with high surfactant adsorption (area/surfactant molecule of 154 Å2) at the CO2–water (C–W) interface which reduced the interfacial tension from ∼40 mN/m to ∼6 mN/m. For C12–14N(CH3)3Cl, these properties enabled stabilization of a C/W foam with an apparent viscosity of 14 mPa·s at 393 K in both a crushed calcium carbonate packed bed (75 μm2 or 76 Darcy) and a capillary tube downstream of the bed. In addition, the partition coefficient of the surfactant between oil and 22% TDS (255 kg/m3) brine was less than 0.15, which would be beneficial for minimizing the loss of the surfactant to an oil phase in applications including enhanced oil recovery and hydraulic fracturing.
A. A. Kmetz, Becker, M. D., Lyon, B. A., Foster, E., Xue, Z., Johnston, K. P., Abriola, L. M., and Pennell, K. D., “Improved Mobility of Magnetite Nanoparticles at High Salinity with Polymers and Surfactants,” Energy & Fuels, vol. 30, no. 3, pp. 1915-1926, 2016. Publisher's VersionAbstract
Engineered nanoparticles have been proposed for use as contrast agents to enhance geophysical characterization of oil and gas reservoirs. Under saline conditions and in the presence of fine materials, nanoparticle mobility in porous media can be severely limited. To address this issue, a series of column experiments was performed to evaluate the ability of selected polymers and surfactants to enhance the transport of magnetite nanoparticles (nMag) coated with cross-linked polymers in the presence of American Petroleum Institute (API) brine (8 wt % NaCl + 2 wt % CaCl2). Aqueous suspensions containing nMag and API brine were injected at pore-water velocities of 2 ± 0.04 m/day or 10 ± 0.40 m/day through columns packed with either 40–50 mesh Ottawa sand or 60–170 mesh crushed Berea sandstone. When nMag (2500 mg/L) was introduced into Ottawa sand, 97% of the injected mass was recovered in the column effluent, indicating high mobility under saline conditions. However, the injection of nMag (2500 mg/L) into crushed Berea sandstone resulted in >60% nMag retention within the column. In order to improve delivery, nMag (2500 mg/L) was co-injected with 1000 mg/L hydroxyethyl cellulose (HEC-10), which increased nMag mobility 2-fold (78% effluent recovery). Co-injection of nMag with 1000 mg/L Gum Arabic or Calfax 16L-35, an anionic surfactant, resulted in slightly lower effluent recoveries of 72% and 69%, respectively. A preflood with 1000 mg/L HEC-10, followed by the injection of nMag alone (2500 mg/L), yielded an additional 20% improvement in nMag mobility (93% effluent recovery), suggesting that HEC-10 screened nMag attachment sites. A multisite nanoparticle transport model that accounts for heterogeneous mineralogy with variable attachment kinetics was able to accurately reproduce the effluent concentration data. Coupled with the observed 7-fold reduction in maximum retention capacity, the model parameter fits provide further evidence to support a site-blocking mechanism. These findings demonstrate the potential for relatively small additions (0.1%) of commercially available polymers and surfactants to greatly improve nMag mobility in porous media
E. E. Ureña-Benavides, Lin, E. L., Foster, E. L., Xue, Z., Ortiz, M., Fei, Y., Larsen, E. S., Kmetz II, A. A., Lyon, B. A., and Bielawski, C. W., “Low Adsorption of Magnetite Nanoparticles with Uniform Polyelectrolyte Coatings in Concentrated Brine on Model Silica and Sandstone,” Industrial & Engineering Chemistry Research, 2016. Publisher's VersionAbstract
In subsurface imaging and oil recovery where temperatures and salinities are high, it is challenging to design polymer-coated nanoparticles with low retention (high mobility) in porous rock. Herein, the grafting of poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylic acid) (poly(AMPS-co-AA)) on magnetic iron oxide nanoparticles was sufficiently uniform to achieve low adsorption on model colloidal silica and crushed Berea sandstone in highly concentrated API brine (8% NaCl and 2% CaCl2 by weight). The polymer shell was grafted via amide bonds to an aminosilica layer, which was grown on silica-coated magnetite nanoparticles. The particles were found to be stable against aggregation in American Petroleum Institute (API) brine at 90 °C for 24 h. For IO nanoparticles with ∼23% polymer content, Langmuir adsorption capacities on colloidal silica and crushed Berea Sandstone in batch experiments were extremely low at only 0.07 and 0.09 mg of IO/m2, respectively. Furthermore, upon injection of a 2.5 mg/mL IO suspension in API brine in a column packed with crushed Berea sandstone, the dynamic adsorption of IO nanoparticles was only 0.05 ± 0.01 mg/m2, which is consistent with the batch experiment results. The uniformity and high concentration of solvated poly(AMPS-co-AA) chains on the IO surfaces provided electrosteric stabilization of the nanoparticle dispersions and also weakened the interactions of the nanoparticles with negatively charged silica and sandstone surfaces despite the very large salinities.
L. Cui, Ma, K., Puerto, M., Abdala, A. A., Tanakov, I., Lu, L. J., Chen, Y., Elhag, A., Johnston, K. P., and Biswal, S. L., “Mobility of ethomeen C12 and carbon dioxide (CO 2) foam at high temperature/high salinity and in carbonate cores,” SPE Journal, 2016. Publisher's VersionAbstract
The low viscosity and density of carbon dioxide (CO2) usually result in the poor sweep efficiency in CO2-flooding processes, especially in heterogeneous formations. Foam is a promising method to control the mobility and thus reduce the CO2 bypass because of the gravity override and heterogeneity of formations. A switchable surfactant, Ethomeen C12, has been reported as an effective CO2-foaming agent in a sandpack with low adsorption on pure-carbonate minerals. Here, the low mobility of Ethomeen C12/CO2 foam at high temperature (120°C), high pressure (3,400 psi), and high salinity [22 wt% of total dissolved solids (TDS)] was demonstrated in Silurian dolomite cores and in a wide range of foam qualities. The influence of various parameters, including aqueous solubility, thermal and chemical stability, flow rate, foam quality, salinity, temperature, and minimum-pressure gradient (MPG), on CO2 foam was discussed. A local-equilibrium foam model, the dry-out foam model, was used to fit the experimental data for reservoir simulation
A. Qajar, Xue, Z., Worthen, A. J., Johnston, K. P., Huh, C., Bryant, S. L., and Prodanović, M., “Modeling fracture propagation and cleanup for dry nanoparticle-stabilized-foam fracturing fluids,” Journal of Petroleum Science and Engineering, vol. 146, pp. 210-221, 2016. Publisher's VersionAbstract
Nanoparticle (NP)-stabilized foams can be generated at extreme water-deficient conditions (with quality as high as 95–99%) and yet with apparent viscosities >100 cP. This makes them greatly appealing for hydraulic fracturing applications, where minimal water consumption and leak-off to the reservoir are desired. Initial assessment of propensities of these novel fluids for fracturing applications requires field scale simulations. However, conventional fracturing models are difficult to employ because they do not consider true foam hydrodynamics. We have developed a mathematical model to simulate the transport of NP-stabilized foams for hydraulic fracturing. The model combines fluid transport in reservoir matrix and fracture with rock mechanics equations and thus allows for considering the effects of foam on fracture dynamics. Gas and water flow with mechanistic accounting of foam generation and coalescence are simulated using population balance models. Transport of nanoparticles through porous media was simulated using single site filtration model. The equations are discretized using finite-difference scheme. Settari’s approach is used to embed fracture’s moving boundary with the matrix to accordingly update transmissibility. Model’s capabilities are verified with examples on fracture growth and fracture clean up processes to illustrate the benefits of using the NP-stabilized high quality foams. Fracture propagation was simulated for water, a conventional viscous fracpad and NP-stabilized foams of different qualities and textures. The simulations confirmed that larger foam viscosity generated wider fractures with smaller fracture half-length. In addition, fracture cleanup simulations show that fracturing fluid cleanup for foam based fracturing fluids could take the order of 10 days as opposed to that of viscous fracpad which could take up to 1000 days; demonstrating the advantage of using dry foams
I. Kim, Worthen, A. J., Lotfollahi, M., Johnston, K. P., DiCarlo, D. A., and Huh, C., “Nanoparticle-Stabilized Emulsions for Improved Mobility Control for Adverse-mobility Waterflooding,” SPE Improved Oil Recovery Conference. Society of Petroleum Engineers, 2016. Publisher's VersionAbstract
The immense nanotechnology advances in other industries provided opportunities to rapidly develop various applications of nanoparticles in the oil and gas industry. In particular, nanoparticle has shown its capability to improve the emulsion stability by generating so-called Pickering emulsion, which is expected to improve EOR processes with better conformance control. Recent studies showed a significant synergy between nanoparticles and very low concentration of surfactant, in generating highly stable emulsions. This study's focus is to exploit the synergy's benefit in employing such emulsions for improved mobility control, especially under high-salinity conditions. Hydrophilic silica nanoparticles were employed to quantify the synergy of nanoparticle and surfactant in oil-in-brine emulsion formation. The nanoparticle and/or the selected surfactant in aqueous phase and decane were co-injected into a sandpack column to generate oil-in-brine emulsions. Four different surfactants (cationic, nonionic, zwitterionic, and anionic) were examined, and the emulsion stability was analyzed using microscope and rheometer. Strong and stable emulsions were successfully generated in the combinations of either cationic or nonionic surfactant with nanoparticles, while the nanoparticles and the surfactant by themselves were unable to generate stable emulsions. The synergy was most significant with the cationic surfactant, while the anionic surfactant was least effective, indicating the electrostatic interactions with surfactant and liquid/liquid interface as a decisive factor. With the zwitterionic surfactant, the synergy effect was not as great as the cationic surfactant. The synergy was greater with the nonionic surfactant than the zwitterionic surfactant, implying that the surfactant adsorption at oil-brine interface can be increased by hydrogen bonding between surfactant and nanoparticle when the electrostatic repulsion is no longer effective. In generating highly stable emulsions for improved control for adverse-mobility waterflooding in harsh-condition reservoirs, we show a procedure to find the optimum choice of surfactant and its concentration to effectively and efficiently generate the nanoparticle-stabilized emulsion exploiting their synergy. The findings in this study propose a way to maximize the beneficial use of nanoparticle-stabilized emulsions for EOR at minimum cost for nanoparticle and surfactant
R. P. Forslund, Mefford, T. J., Hardin, W. G., Alexander, C. T., Johnston, K. P., and Stevenson, K. J., “Nanostructured LaNiO3 perovskite electrocatalyst for enhanced urea oxidation,” ACS Catalysis, vol. 6, no. 8, pp. 5044-5051, 2016. Publisher's VersionAbstract
Urea electrooxidation has attracted considerable interest as an alternative anodic reaction in the electrochemical generation of hydrogen due to both the lower electrochemical potential required to drive the reaction and also the possibility of eliminating a potentially harmful substance from wastewater during hydrogen fuel production. Nickel and nickel-containing oxides have shown activities comparable to those of precious-metal catalysts for the electrooxidation of urea in alkaline conditions. Herein, we investigate the use of nanostructured LaNiO3 perovskite supported on Vulcan carbon XC-72 as an electrocatalyst. This catalyst exhibits an exceptionally high mass activity of ca. 371 mA mgox–1 and specific activity of 2.25 A mg–1 cmox–2 for the electrooxidation of urea in 1 M KOH, demonstrating the potential applications of Ni-based perovskites for direct urea fuel cells and low-energy hydrogen production. While LaNiO3 is shown to be stable at low overpotentials, through in-depth mechanistic studies the catalyst surface was observed to restructure and there was apparent CO2 poisoning of the LaNiO3 upon extended cycling, a result that may be extended to other Ni-based systems.
Y. Chen, Elhag, A. S., Reddy, P. P., Chen, H., Cui, L., Worthen, A. J., Ma, K., Quintanilla, H., Noguera, J. A., and Hirasaki, G. J., “Phase behavior and interfacial properties of a switchable ethoxylated amine surfactant at high temperature and effects on CO 2-in-water foams,” Journal of colloid and interface science, vol. 470, pp. 80-91, 2016. Publisher's VersionAbstract
The interfacial properties for surfactants at the supercritical CO2–water (C–W) interface at temperatures above 80 °C have very rarely been reported given limitations in surfactant solubility and chemical stability. These limitations, along with the weak solvent strength of CO2, make it challenging to design surfactants that adsorb at the C–W interface, despite the interest in CO2-in-water (C/W) foams (also referred to as macroemulsions). Herein, we examine the thermodynamic, interfacial and rheological properties of the surfactant C12–14N(EO)2 in systems containing brine and/or supercritical CO2 at elevated temperatures and pressures. Because the surfactant is switchable from the nonionic state to the protonated cationic state as the pH is lowered over a wide range in temperature, it is readily soluble in brine in the cationic state below pH 5.5, even up to 120 °C, and also in supercritical CO2 in the nonionic state. As a consequence of the affinity for both phases, the surfactant adsorption at the CO2–water interface was high, with an area of 207 Å2/molecule. Remarkably, the surfactant lowered the interfacial tension (IFT) down to ∼5 mN/m at 120 °C and 3400 psia (23 MPa), despite the low CO2 density of 0.48 g/ml, indicating sufficient solvation of the surfactant tails. The phase behavior and interfacial properties of the surfactant in the cationic form were favorable for the formation and stabilization of bulk C/W foam at high temperature and high salinity. Additionally, in a 1.2 Darcy glass bead pack at 120 °C, a very high foam apparent viscosity of 146 cP was observed at low interstitial velocities given the low degree of shear thinning. For a calcium carbonate pack, C/W foam was formed upon addition of Ca2+ and Mg2+ in the feed brine to keep the pH below 4, by the common ion effect, in order to sufficiently protonate the surfactant. The ability to form C/W foams at high temperatures is of interest for a variety of applications in chemical synthesis, separations, materials science, and subsurface energy production.
I. Kim, Worthen, A. J., Johnston, K. P., DiCarlo, D. A., and Huh, C., “Size-dependent properties of silica nanoparticles for Pickering stabilization of emulsions and foams,” Journal of Nanoparticle Research, vol. 18, no. 4, pp. 1-12, 2016. Publisher's VersionAbstract
Nanoparticles are a promising alternative to surfactants to stabilize emulsions or foams in enhanced oil recovery (EOR) processes due to their effectiveness in very harsh environments found in many of the oilfields around the world. While the size-dependent properties of nanoparticles have been extensively studied in the area of optics or cellular uptake, little is known on the effects of nanoparticle size on emulsion/foam generation, especially for EOR applications. In this study, silica nanoparticles with four different sizes (5, 12, 25, and 80 nm nominal diameter) but with the same surface treatment were employed to test their emulsion or foam generation behavior in high-salinity conditions. The decane-in-brine emulsion generated by sonication or flowing through sandpack showed smaller droplet size and higher apparent viscosity as the nanoparticle size decreased. Similarly, the CO2-in-brine foam generation in sandstone or sandpacks was also significantly affected by the nanoparticle size, exhibiting higher apparent foam viscosity as the nanoparticle size decreased. In case of foam generation in sandstone cores with 5 nm nanoparticles, a noticeable hysteresis occurred when the flow velocity was initially increased and then decreased, implying a strong foam generation initially; and then the trapping of the generated foam in the rock pores, as the flow velocity decreased. On the other hand, weak foams stabilized with larger nanoparticles indicated a rapid coalescence of bubbles which prevented foam generation. Overall, stable emulsions/foams were achievable by the smaller particles as a result of greater diffusivity and/or higher number concentration, thus allowing more nanoparticles with higher surface area to volume ratio to be adsorbed at the fluid/fluid interfaces of the emulsion/foam dispersion. Graphical abstract
G. Jian, Puerto, M. C., Wehowsky, A., Dong, P., Johnston, K. P., Hirasaki, G. J., and Biswal, S. L., “Static Adsorption of an Ethoxylated Nonionic Surfactant on Carbonate Minerals,” Langmuir, vol. 32, no. 40, pp. 10244-10252, 2016. Publisher's VersionAbstract
The static adsorption of C12–14E22, which is a highly ethoxylated nonionic surfactant, was studied on different minerals using high-performance liquid chromatography (HPLC) combined with an evaporative light scattering detector (ELSD). Of particular interest is the surfactant adsorption in the presence of CO2 because it can be used for foam flooding in enhanced oil recovery applications. The effects of the mineral type, impurities, salinity, and temperature were investigated. The adsorption of C12–14E22 on pure calcite was as low as 0.01 mg/m2 but higher on dolomite depending on the silica and clay content in the mineral. The adsorption remained unchanged when the experiments were performed using a brine solution or 0.101 MPa (1 atm) CO2, which indicates that electrostatic force is not the governing factor that drives the adsorption. The adsorption of C12–14E22 on silica may be due to hydrogen bonding between the oxygen in the ethoxy groups of the surfactant and the hydroxyl groups on the mineral surface. Additionally, thermal decomposition of the surfactant was severe at 80 °C but can be inhibited by operating in a reducing environment. Under reducing conditions, adsorption of C12–14E22increased at higher temperatures
A. J. Worthen, Tran, V., Cornell, K. A., Truskett, T. M., and Johnston, K. P., “Steric stabilization of nanoparticles with grafted low molecular weight ligands in highly concentrated brines including divalent ions,” Soft matter, vol. 12, no. 7, pp. 2025-2039, 2016. Publisher's VersionAbstract
Whereas numerous studies of stabilization of nanoparticles (NPs) in electrolytes have examined biological fluids, the interest has grown recently in media with much higher ionic strengths including seawater and brines relevant to environmental science and subsurface oil and gas reservoirs. Given that electrostatic repulsion is limited at extremely high ionic strengths due to charge screening, we have identified ligands that are well solvated in concentrated brine containing divalent cations and thus provide steric stabilization of silica nanoparticles. Specifically, the hydrodynamic diameter of silica nanoparticles with grafted low molecular weight ligands, a diol ether, [3-(2,3-dihydroxypropoxy)propyl]-trimethoxysilane, and a zwitterionic sulfobetaine, 3-([dimethyl(3-trimethoxysilyl)propyl]ammonio)propane-1-sulfonate, is shown with dynamic light scattering to remain essentially constant, indicating lack of aggregation, at room temperature and up to 80 °C for over 30 days. An extended DLVO model signifies that steric stabilization is strongly dominant against van der Waals attraction for ∼10 nm particles given that these ligands are well solvated even in highly concentrated brine. In contrast, polyethylene glycol oligomers do not provide steric stabilization at elevated temperatures, even at conditions where the ligands are soluble, indicating complicating factors including bridging of the ether oxygens by divalent cations
V. Prigiobbe, Worthen, A. J., Johnston, K. P., Huh, C., and Bryant, S. L., “Transport of Nanoparticle-Stabilized CO_2-Foam in Porous Media,” Transport in Porous Media, vol. 111, no. 1, pp. 265-285, 2016. Publisher's VersionAbstract
Foam is injected in the subsurface to improve mobility control through the increase in the effective gas viscosity, e.g., in CO2">22-based enhanced oil recovery processes. As fine-textured foam has higher viscosity, it is envisaged to achieve an optimal foam texture and to maintain it for the entire period of an application. However, mechanisms of foam formation and destruction, which affect texture, are difficult to regulate. In this study, we investigate the synergic effect of nanoparticles and surfactant on the foam texture and the effective gas viscosity (&#x03BC;gf">μfgμgf) during transport in a porous medium. Experiments using glass-bead packs were performed injecting CO2">22 and a solution containing either only surfactant or surfactant and nanoparticles. During each experiment, the pressure drop (&#x0394;p">ΔpΔp) through the porous medium was measured to follow the generation of the foam. A two-phase flow mechanistic model combining the mass conservation law for water and CO2">22 and the population balance equation of the lamellae was implemented to analyze the experiments and predict foam transport under the investigated conditions. The constitutive equations for foam generation and destruction were based on the dominant role of pressure gradient on lamella division and of capillary pressure on bubble coalescence, and their parameters were estimated using pressure drop measurements. Both equations were formulated for a surfactant-stabilized foam, and it was the aim of this work to understand their validity also for the case of a nanoparticle-stabilized foam. The experiments compare well with the theory showing that a foam stabilized with nanoparticles and surfactant can be modeled as a surfactant-stabilized foam. Overall, &#x0394;p">ΔpΔp increases smoothly while the foam forms and, upon breakthrough, it stabilizes around a constant value while approaching steady state. During this phase, oscillations occur, particularly when high-quality foam is generated as the system is close to its critical conditions of capillary pressure and water saturation. When steady state is reached, the effective gas viscosity varies with fg">fgfg and solution composition and significantly increases when surfactant and nanoparticles are added. The maximum value of &#x03BC;gf">μfgμgf is 0.110 Pa s for fg">fgfg = 0.75, which is almost twofold of the maximum value attained when only a surfactant is used, corresponding to 0.067 Pa s at fg">fgfg = 0.4. This suggests that when nanoparticles and surfactant are employed, they can favor the formation of a strong high-quality CO2">22-foam.

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