Shape transitions in supercritical CO₂ microemulsions induced by hydrotropes

The ability to induce morphological transitions in water-in-oil (w/o) and water-in-CO₂ (w/c) microemulsions stabilized by a trichain anionic surfactant 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2- sulfonate (TC14) with simple hydrotrope additives has been investigated. High-pressure small-angle neutron scattering (SANS) has revealed the addition of a small mole fraction of hydrotrope can yield a significant elongation in the microemulsion water droplets. For w/o systems, the degree of droplet growth was shown to be dependent on the water content, the hydrotrope mole fraction, and chemical structure, whereas for w/c microemulsions a similar, but less significant, effect was seen. The expected CO₂ viscosity increase from such systems has been calculated and compared to related literature using fluorocarbon chain surfactants. This represents the first report of hydrotrope-induced morphology changes in w/c microemulsions and is a significant step forward toward the formation of hydrocarbon worm-like micellar assemblies in this industrially relevant solvent.