Tuning Surface Chemistry and Ionic Strength to Control Nanoparticle Adsorption and Elastic Dilational Modulus at Air-Brine Interface.

The relationship between the interfacial rheology of nanoparticle (NP) laden air-brine interfaces and NP adsorption and interparticle interactions is not well understood, particularly as a function of the surface chemistry and salinity. Herein, a nonionic ether diol on the surface of silica NPs provides steric stabilization in bulk brine and at the air-brine interface, whereas a second smaller underlying hydrophobic ligand raises the hydrophobicity to promote NP adsorption. The level of NPs adsorption at steady state is sufficient to produce an interface with a relatively strong elastic dilational modulus E' = dγ/d ln A. However, the interface is ductile with a relatively slow change in E' as the interfacial area is varied over a wide range during compression and expansion. In contrast, for silica NPs stabilized with only a single hydrophobic ligand, the interfaces are often more fragile and may fracture with small changes in area. The presence of concentrated divalent cations improves E' and ductility by screening electrostatic dipolar repulsion and strengthening the attractive forces between nanoparticles. The ability to tune the interfacial rheology with NP surface chemistry is of great interest for designing more stable gas/brine foams.

Tuning Nanoparticle Surface Chemistry and Interfacial Properties for Highly Stable Nitrogen-In-Brine Foams.

The design of surface chemistries on nanoparticles (NPs) to stabilize gas/brine foams with concentrated electrolytes, especially with divalent ions, has been elusive. Herein, we tune the surface of 20 nm silica NPs by grafting a hydrophilic and a hydrophobic ligand to achieve two seemingly contradictory goals of colloidal stability in brine and high NP adsorption to yield a viscoelastic gas-brine interface. Highly stable nitrogen/water (N2/brine) foams are formed with CaCl2 concentrations up to 2% from 25 to 90 °C. The viscoelastic gas-brine interface retards drainage of the lamellae, and the high dilational elasticity arrests coarsening (Ostwald ripening) with no observable change in foam bubble size over 48 h. The ability to design NP-laden viscoelastic interfaces for highly stable foams, even with high divalent ion concentrations, is of fundamental mechanistic interest for a broad range of foam applications and in particular foams for CO2 sequestration and enhanced oil recovery.

Self-Association of Rafoxanide in Aqueous Media and Its Application in Preparing Amorphous Solid Dispersions.

Our primary objective is to characterize the self-association of rafoxanide in alkaline media. The second objective is to illustrate the feasibility of using rafoxanide micellar solution as the feed solution to prepare amorphous solid dispersion via spray drying. Rafoxanide is a poorly water-soluble drug. It is a weak acid, and its poor aqueous solubility is due to its hydrophobicity. The surface-active property of rafoxanide has not been previously reported. It was discovered that the addition of a small percentage of organic solvents is required to elevate the solubility of rafoxanide above the critical micelle concentration to allow for the formation of micelles. Our fluorescence decay study confirms the self-association of rafoxanide in a cosolvent consisting of 70%, v/v, NaOH solution and 30%, v/v, acetone. The position of each functional group in the micellar structures using the 1H NMR technique was identified. The critical micelle concentration of rafoxanide in the cosolvent is determined to be 302 µg/mL using a surface tension method. The solubility of rafoxanide in 0.1 N NaOH solution is less than 11 µg/mL. Interestingly, the apparent solubility increased to 38,400 µg/mL in the presence of 30% acetone as the result of micelle formation. This unique solubility characteristic makes it feasible to prepare rafoxanide amorphous solid dispersions by spray drying a predominantly aqueous (70% 0.1 N NaOH solution and 30% acetone) based feed solution. Povidone and copovidone were both used as polymeric carriers. Based on solid-state characterization, including differential scanning calorimetry, X-ray powder diffraction, and hot-stage polarized light microscopy, our results indicate that rafoxanide solid dispersions prepared using this novel process are amorphous. Approximately 750-fold increase in the concentration of rafoxanide in aqueous media at pH 6.8 was achieved with the amorphous solid dispersions.

Ultradry Carbon Dioxide-in-Water Foams with Viscoelastic Aqueous Phases.

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.

Origins of pressure dependent permeability in unconventional hydrocarbon reservoirs.

Unconventional hydrocarbon assets represent a rapidly expanding proportion of North American oil and gas production. Similar to the incipient phase of conventional oil production at the turn of the twentieth century, there are ample opportunities to improve production efficiency. In this work we demonstrate that pressure dependent permeability degradation exhibited by unconventional reservoir materials is due to the mechanical response of a few commonly encountered microstructural constituents. In particular, the mechanical response of unconventional reservoir materials may be conceptualized as the superposed deformation of matrix (or ~ cylindrical/spherical), and compliant (or slit) pores. The former are representative of pores in a granular medium or a cemented sandstone, while the latter represent pores in an aligned clay compact or a microcrack. As a result of this simplicity, we demonstrate that permeability degradation is accounted for through a weighted superposition of conventional permeability models for these pore architectures. This approach permits us to conclude that the most severe pressure dependence is due to imperceptible bedding parallel delamination cracks in the oil bearing argillaceous (clay-rich) mudstones. Finally, we demonstrate that these delaminations tend to populate layers that are enriched with organic carbon. These findings are a basis for improving recovery factors through the development of new completion techniques to exploit, then mitigate pressure dependent permeability in practice.

Elastic gas/water interface for highly stable foams with modified anionic silica nanoparticles and a like-charged surfactant.

HYPOTHESIS: Surface active anionic nanoparticles (NPs) with strategically designed covalent ligands may be combined with a liked-charged surfactant to form a highly elastic gas-water interface leading to highly stable gas/water foams. EXPERIMENTS: The colloidal stability of the NPs was determined by dynamic light scattering, and the surface elastic dilational modulus E' of the interface by sinusoidal oscillation of a pendant droplet at 0.1 Hz, which was superimposed on large-amplitude compression-expansion cycles. The foam stability was measured with optical microscopy of the bubble size distribution and from the macroscopic foam height. FINDINGS: The NPs played the key role the formation of a highly elastic air-water interface with a high E' despite a surfactant level well above the critical micelle concentration. Unlike the case for most previous studies, the NP amphiphilicity was essentially independent of the surfactant given the very low adsorption of the surfactant on the like-charged NP surfaces. With high E' values, both coalescence and coarsening were reduced leading to highly foam up to 80 °C. However, the surfactant facilitated foam generation at much lower shear rates than with NPs alone. The tuning of NP surfaces with ligands for colloidal stability in brine and simultaneously high amphiphilicity at the gas-water interface, over a wide range in surfactant concentration, is of broad interest for enabling the design of highly stable foams.

Effect of surface chemistry of silica nanoparticles on contact angle of oil on calcite surfaces in concentrated brine with divalent ions.

HYPOTHESIS: For an oil droplet on calcite with an intervening brine film, the water contact angle θw may be reduced markedly (greater water wetness) with surface modified silica nanoparticles (NP). Modification with cationic, anionic, and nonionic ligands may be used to control the nanoparticle adsorption and interactions at the oil-brine and brine-calcite interfaces to influence the rate and degree of reduction in θw. EXPERIMENTS: The colloidal stability at 25 °C was determined in concentrated divalent brine (8 wt% NaCl and 2 wt% CaCl2) with dynamic light scattering, and the NP adsorption was determined on calcite. The NP adsorption at the oil-brine interface was characterized with the elastic dilational modulus. θw was measured for model decane-stearic acid droplets and crude oil droplets on calcite from 25 to 80 °C. FINDINGS: The fastest rate and greatest extent of reduction in θw for grafted ligands followed the order: cationic quaternary trimethylamine > sulfonate > methyl phosphonate > gluconamide. New mechanisms for reduction in θw were demonstrated on the basis of changes in interactions from NP adsorption at each interface. The greatest efficacy for the cationic NPs results from the weakest adsorption on calcite, steric repulsion at the three-phase contact line and the greatest desorption of carboxylate surfactants from the calcite.

Carbon dioxide-in-oil emulsions stabilized with silicone-alkyl surfactants for waterless hydraulic fracturing.

The design of surfactants for CO2/oil emulsions has been elusive given the low CO2-oil interfacial tension, and consequently, low driving force for surfactant adsorption. Our hypothesis is that waterless, high pressure CO2/oil emulsions can be stabilized by hydrophobic comb polymer surfactants that adsorb at the interface and sterically stabilize the CO2 droplets. The emulsions were formed by mixing with an impeller or by co-injecting CO2 and oil through a beadpack (CO2 volume fractions (ϕ) of 0.50-0.90). Emulsions were generated with comb polymer surfactants with a polydimethylsiloxane (PDMS) backbone and pendant linear alkyl chains. The C30 alkyl chains are CO2-insoluble but oil soluble (oleophilic), whereas PDMS with more than 50 repeat units is CO2-philic but only partially oleophilic. The adsorbed surfactants sterically stabilized CO2 droplets against Ostwald ripening and coalescence. The optimum surfactant adsorption was obtained with a PDMS degree of polymerization of ∼88 and seven C30 side chains. The emulsion apparent viscosity reached 18 cP at a ϕ of 0.70, several orders of magnitude higher than the viscosity of pure CO2, with CO2 droplets in the 10-150 µm range. These environmentally benign waterless emulsions are of interest for hydraulic fracturing, especially in water-sensitive formations.

Viscoelastic diamine surfactant for stable carbon dioxide/water foams over a wide range in salinity and temperature.

HYPOTHESIS: The viscosity and stability of CO2/water foams at elevated temperature can be increased significantly with highly viscoelastic aqueous lamellae. The slow thinning of these viscoelastic lamellae leads to greater foam stability upon slowing down Ostwald ripening and coalescence. In the aqueous phase, the viscoelasticity may be increased by increasing the surfactant tail length to form more entangled micelles even at high temperatures and salinity. EXPERIMENTS: Systematic measurements of the steady state shear viscosity of aqueous solutions of the diamine surfactant (C16-18N(CH3)C3N(CH3)2) were conducted at varying surfactant concentrations and salinity to determine the parameters for formation of entangled wormlike micelles. The apparent viscosity and stability of CO2/water foams were compared for systems with viscoelastic entangled micellar aqueous phases relative to those with much less viscous spherical micelles. FINDINGS: We demonstrated for the first time stable CO2/water foams at temperatures up to 120 °C and CO2 volumetric fractions up to 0.98 with a single diamine surfactant, C16-18N(CH3)C3N(CH3)2. The foam stability was increased by increasing the packing parameter of the surfactant with a long tail and methyl substitution on the amine to form entangled viscoelastic wormlike micelles in the aqueous phase. The foam was more viscous and stable compared to foams with spherical micelles in the aqueous lamellae as seen with C12-14N(EO)2 and C16-18N(EO)C3N(EO)2.

High temperature ultralow water content carbon dioxide-in-water foam stabilized with viscoelastic zwitterionic surfactants.

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 120cP 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 ∼35µm 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 CO2 flow patterns), and possibly even hydraulic fracturing with minimal use of water to reduce the requirements for wastewater disposal.