Adsorption, organization, and rheology of catanionic layers at the air/water interface.

We have investigated the adsorption and organization at the air/water interface of catanionic molecules released from a dispersion of solid-like catanionic vesicles composed of myristic acid and cetyl trimethylammonium chloride at the 2:1 ratio. These vesicles were shown recently to be promising foam stabilizers. Using Brewster angle microscopy, we observed the formation of a catanionic monolayer at the air/water interface composed of liquid-condensed domains in a liquid-expanded matrix. Further adsorption of catanionic molecules forced them to pack, thereby forming a very dense monolayer that prevented further vesicle rupture by avoiding contact of the vesicles with air. Moreover, confocal fluorescence microscopy revealed the presence of layers of intact vesicles that were progressively creaming toward this catanionic monolayer; the surface tension of the vesicle dispersion remained constant upon creaming. The catanionic monolayer behaved as a soft glassy material, an amorphous solid with time- and temperature-dependent properties. Using interfacial oscillatory rheology, we found that the monolayer relaxed mechanical stresses in seconds and melted at a temperature very close to the melting transition temperature of the vesicle bilayers. These results have potential application in the design of smart foams that have temperature-tunable stability.