Viscosity and stability of ultra-high internal phase CO2-in-water foams stabilized with surfactants and nanoparticles with or without polyelectrolytes.

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.

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.

Characterization of micro- and mesoporous materials using accelerated dynamics adsorption.

Porosimetry is a fundamental characterization technique used in development of new porous materials for catalysis, membrane separation, and adsorptive gas storage. Conventional methods like nitrogen and argon adsorption at cryogenic temperatures suffer from slow adsorption dynamics especially for microporous materials. In addition, CO2, the other common probe, is only useful for micropore characterization unless being compressed to exceedingly high pressures to cover all required adsorption pressures. Here, we investigated the effect of adsorption temperature, pressure, and type of probe molecule on the adsorption dynamics. Methyl chloride (MeCl) was used as the probe molecule, and measurements were conducted near room temperature under nonisothermal condition and subatmospheric pressure. A pressure control algorithm was proposed to accelerate adsorption dynamics by manipulating the chemical potential of the gas. Collected adsorption data are transformed into pore size distribution profiles using the Horvath-Kavazoe (HK), Saito-Foley (SF), and modified Kelvin methods revised for MeCl. Our study shows that the proposed algorithm significantly speeds up the rate of data collection without compromising the accuracy of the measurements. On average, the adsorption rates on carbonaceous and aluminosilicate samples were accelerated by at least a factor of 4-5.