Rheological Characterization of Mixed Surfactant Films at Droplet Interfaces via Micropipette Aspiration

Cationic and anionic surfactant mixtures can form viscous films that dominate the rheology and stability of micrometer-sized droplet suspensions. In this work, we use micropipette aspiration to study the mechanical properties of mixed surfactant surface films of anionic sodium dodecyl sulfate (SDS) and cationic dodecylamine hydrochloride (DAH) on alkane and lipid droplets. For octane droplets, SDS was found to decrease the surface tension until a minimum of 5 ± 1 mJ/m² was reached after the critical micelle concentration (cmc). The surface viscosity of the droplets was found to be on the order of 10^-3 mN s/m at an SDS concentration of 10 mM. An addition of 0.2 mM of DAH was found to increase this viscosity to a peak of 0.24 ± 0.01 mN s/m. Similar to octane, the surface tension of dodecane decreased to a value of 7.7 ± 0.4 mJ/m² at SDS concentrations above cmc. Unlike with octane, however, the dodecane droplets had a significant surface viscosity of 0.37 ± 0.01 mN s/m when only the 10 mM SDS film was present. An addition of DAH caused a decrease in this viscosity initially, before rising to a peak viscosity of 0.45 ± 0.01 mN s/m at a DAH concentration of 0.15 mM. We speculate that the peaks in viscosities were the result of the completions of a phase change associated with microcrystalline SDS/DAH grains growing in the film at the surface of the droplets. Fluorescence microscopy and visual observations provided further evidence that these films can show rigid microcrystalline-like structure. Further work done with soybean oil in the same conditions and with a lipid film, simulating biological lipid droplets, confirmed that lipid droplets behave rheologically similar to alkanes in the presence of these mixed surfactant and lipid films. These results imply that droplet mechanics may be heavily influenced by the presence of microcrystalline grains in the oil-water systems with complex surfactant mixtures.