Emulsions and microemulsions of water and carbon dioxide: Novel surfactants and stabilization mechanisms

During the last two decades colloid and interface science in the field of supercritical fluid technology has brought enormous potentials in the utilization of supercritical carbon dioxide as an environmentally benign solvent. Liquid or supercritical CO2 exhibits solvent properties that are tunable with pressure, and is essentially nontoxic and nonflammable. Emulsions and microemulsions of water and CO2, whether in the form of water-in-CO 2 (w/c) or CO2-in-water (c/w), offer new possibilities for separations on the basis of polarity, and as media for reactions between polar and nonpolar molecules. For the first time, formation of thermodynamically stable c/w microemulsions was characterized by dynamic light scattering (DLS) technique. High-pressure carbon dioxide swells potassium carboxylate perfluoropolyether (PFPE-K) cylindrical micelles in water, elongating the micelles significantly from 20 up to 80 nm. As the micelles swell to form microemulsions, the solubility of pyrene increases by a factor of ca. 10. It was demonstrated w/c microemulsions may be formed with nonionic hydrocarbon surfactant. Methylated branched tail of the surfactant enhances formation of stable w/c microemulsions as it raises surfactant solubility in CO2, shifts the curvature towards bending about water, and weakens interdroplet interactions by reducing overlap between surfactant tails. As a novel medium for reactions, w/c microemulsions with low water content are utilized for the synthesis of TiO2 nanoparticles via the controlled hydrolysis of titanium tetraisopropoxide. The size of particles could be controlled by adjusting the water-to-surfactant ratio (wo). Based on DLS measurements, the size of TiO2 particles was comparable to that of the microemulsion droplets indicating steric stabilization was sufficient during the rapid hydrolysis. Finally, electrostatic repulsion between water droplets of w/c emulsion was explored as an alternative to the steric stabilization mechanism. Negative zeta-potentials as high as 70 mV are measured for emulsion droplets by microelectrophoresis. Unprecedented crystalline structure of the droplet array with a spacing of several droplet-diameters is identified by microscopy, and investigated in terms of a balance between long-range electrostatic repulsions acting through the low dielectric medium (epsilonr = 1.5 for high pressure CO2) and the gravitational force which tends to decrease inter-droplet distances.