Anisotropic reversed micelles with fluorocarbon-hydrocarbon hybrid surfactants in supercritical CO₂

Previous work (M. Sagisaka, et al. Langmuir 31 (2015) 7479-7487), showed the most effective fluorocarbon (FC) and hydrocarbon (HC) chain lengths in the hybrid surfactants FCm-HCn (sodium 1-oxo-1-[4-(perfluoroalkyl)phenyl]alkane-2-sulfonates, where m = FC length and n = HC length) were m and n = 6 and 4 for water solubilization, whereas m 6 and n 6, or m 6 and n 5, were optimal chain lengths for reversed micelle elongation in supercritical CO₂. To clarify why this difference of only a few methylene chain units is so effective at tuning the solubilizing power and reversed micelle morphology, nanostructures of water-in-CO₂ (W/CO₂) microemulsions were investigated by high-pressure small-angle neutron scattering (SANS) measurements at different water-to-surfactant molar ratios (W₀) and surfactant concentrations. By modelling SANS profiles with cylindrical and ellipsoidal form factors, the FC6-HCn/W/CO₂ microemulsions were found to increase in size with increasing W₀ and surfactant concentration. Ellipsoidal cross-sectional radii of the FC6-HC4/W/CO₂ microemulsion droplets increased linearly with W₀, and finally reached ∼39 Å and ∼78 Å at W₀ = 85 (close to the upper limit of solubilizing power). These systems appear to be the largest W/CO₂ microemulsion droplets ever reported. The aqueous domains of FC6-HC6 rod-like reversed micelles increased in size by 3.5 times on increasing surfactant concentration from 35 mM to 50 mM: at 35 mM, FC6-HC5 formed rod-like reversed micelles 5.3 times larger than FC6-HC6. Interestingly, these results suggest that hybrid HC-chains partition into the microemulsion aqueous cores with the sulfonate headgroups, or at the W/CO₂ interfaces, and so play important roles for tuning the W/CO₂ interfacial curvature. The super-efficient W/CO₂-type solubilizer FC6-HC4, and the rod-like reversed micelle forming surfactant FC6-HC5, represent the most successful cases of low fluorine content additives. These surfactants facilitate VOC-free, effective and energy-saving CO₂ solvent systems for applications such as extraction, dyeing, dry cleaning, metal-plating, enhanced oil recovery and organic/inorganic or nanomaterial synthesis.