Formation of Water-in-Carbon Dioxide Microemulsions with a Cationic Surfactant:  A Small-Angle Neutron Scattering Study

Abstract

The formation of water-in-carbon dioxide microemulsions with a cationic perfluoropolyether trimethylammonium acetate surfactant, PFPE−C(O)−NH−CH 2 −N + (CH 3 ) 3 CH 3 COO -, is reported over a range of temperatures (25−90 °C) and pressures (87.3−415 bar). Spherical droplets are observed by SANS with radii ranging from 16 to 36 Å for water-to-surfactant molar ratios ( W o ) from 9.5 to 28. Porod analysis of the SANS data indicates an area of approximately 60 Å 2 /surfactant molecule at the water−CO 2 interface, in reasonable agreement with the value of 72 Å 2 determined from the change in the droplet radius with W o . The CO 2 -phobic functionality between the surfactant headgroup and perfluoropolyether tail reduces CO 2 penetration of the tails, resulting in a smaller area/surfactant than in the case of an anionic perfluoropolyether surfactant [ Langmuir 1997, 13, 3934]. A relatively rigid film, with a mean film rigidity (2 K + K̄ ) of approximately 1 k B T, along with the strong partitioning of the surfactant toward CO 2 versus water, lead to the small, rigid, spherical water droplets in CO 2 .