Atomic Force Microscopy Force Mapping Analysis of an Adsorbed Surfactant above and below the Critical Micelle Concentration

Force curves collected using an atomic force microscope (AFM) in the presence of adsorbed surfactants are often used to draw conclusions about adsorbed film packing, rigidity, and thickness. However, some noteworthy features of such force curve characteristics have yet to be thoroughly investigated and explained. In this work, we collected force curves from tetradecyltrimethylammonium bromide films adsorbed on highly oriented pyrolytic graphite (HOPG), silica, and silica that had been hydrophobized by functionalization with dichlorodimethyl silane. Breakthrough events in the force curves from several different trials were compared to show that the breakthrough distance, often reported as the adsorbed film thickness, increased with concentration below the critical micelle concentration (CMC) but was approximately 3.5 nm on all surfaces between 2× and 10× CMC; an unexpected result because of the different surface chemistries for the three surfaces. We employed an AFM probe with a different force constant ( k) value as well as a colloidal probe and the breakthrough distance remained approximately 3.5 nm in all cases. Gradient mapping, a variant of force mapping, was also implemented on the three surfaces and resulted in a new technique for visualizing adsorbed surfactant in situ. The resulting maps showed patches of adsorbed surfactant below the CMC and revealed that with increasing concentration, the size of the patches increased resulting in full coverage near and above the CMC. These results are, to our knowledge, the first time force mapping has been used to spatially track patches of adsorbed surfactant. Finally, layers of surfactants on an AFM tip were investigated by collecting a force map on a single AFM tip using the tip of a separate AFM probe. A breakthrough event was observed between the tips, indicating that a layer of surfactant was present on at least one, if not both tips.