Mechanical and thermodynamic properties of surfactant aggregates at the solid–liquid interface

Surfactants are widely used to stabilize colloidal systems in a variety of industrial applications through the formation of self-assembled aggregates at the solid–liquid interface. Previous studies have reported that the control of surfactant-mediated slurry stability can be achieved through the manipulation of surfactant chain length and concentration. However, a fundamental understanding of the mechanical and energetic properties of these aggregates, which may aid in the molecular-level design of these systems, is still lacking. In this study, experimentally measured force/distance curves between an atomic force microscope (AFM) tip and self-assembled surfactant aggregates on mica or silica substrates at concentrations higher than the bulk critical micelle concentration (CMC) were used to determine their mechanical and thermodynamic properties. The experimental curves were fitted to a model which describes the interaction between a hard sphere (tip) and a soft substrate (surfactant structures) based on a modified Hertz theory for the case of a thin elastic layer on a rigid substrate. The calculated mechanical properties were found to be in the same order of magnitude as those reported for rubber-like materials (e.g., polydimethylsiloxane (PDMS)). By integrating the force/distance curves, the energy required for breaking the surface aggregates was also calculated. These values are close to those reported for bulk–micelle formation.