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.

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.