Comparison of morphology and mechanical properties of surfactant aggregates at water-silica and water-graphite interfaces from molecular dynamics simulations

Cationic surfactants are important for a wide range of applications, including controlled drug delivery systems, emulsifiers, and chemical mechanical polishing. It is therefore important to better understand surfactant structure and properties at the solid-liquid interface. Here, classical molecular dynamics simulations with empirical potentials are used to compare the structures and mechanical properties of cationic surfactant micelles at hydrophobic (graphite) and hydrophilic (silica) surface-water interfaces. In particular, the morphology of monolayers and bilayers of C₁₂TAB (n- dodecyltrimethylammoniumbromide) at these interfaces, and their responses to atomic force microscopy indentation, are examined. The simulations predict that surfactant monolayers and bilayers on silica evolve into a spherical micelle structure, in agreement with theoretical models of surfactant morphology. In contrast, surfactant monolayers on graphite evolve into a hemi-cylindrical structure, in agreement with experimental findings. In the simulated indentation of the micelle/silica system, the spherical micelle breaks apart and forms a surfactant monolayer. The indentation force curve has a maximum value of 2.25 nN. On the other hand, the simulated indentation of the micelle/graphite system causes the hemi-cylindrical micelle structure to break apart and the surfactant tails to wrap around the graphite indenter. The indentation force curve has a maximum value of 13 nN.