Effect of the chain-length compatibility of surfactants and mechanical properties of mixed micelles on surfaces.

Force/distance curves for silicon nitride tip/flat silica or alumina coated by a layer of mixed micelles of cationic/anionic surfactant are measured by using AFM. Mixtures of SDS/C(n)TAB (with molecular ratios of 3:1 and 20:1) and C(n)TAB/SDS (with molecular ratio of 85:15) were used for alumina and silica substrates, respectively. The number of carbon atoms per C(n)TAB molecule, n, was in the range of 8 to 16. On the basis of the force/distance curves, the elastic modulus, E, and yield strength, Y, of surface micelles are calculated. It is shown that in surfactant mixtures containing SDS the maximal repulsive force (the barrier F(bar)) at which the tip punctured the micelles, as well as the magnitudes of E and Y, attained the maximal values for C(12)TAB ( i.e., when the hydrocarbon chain lengths of two oppositely charged surfactants are the same). Obviously, it can be related to the highest density structure of these micelles. Note that the literature data for the surface micelles from pure C(n)TAB solutions demonstrate a monotonic dependence of F(bar), E, and Y on n in the range of n = 8-16, whereas the oppositely charged mixed surfactant systems yield much higher values of F(bar), E, and Y than does an equivalent chain length from the homologue series plots. The results obtained for mechanical characteristics of mixed micelles at the surface are compared with the results for the relaxation time, tau(2), that characterizes the lifetime (and therefore structure) of the bulk micelles. Both the dependence of F(bar), E, and Y on n for the surface mixed micelles and tau(2) on n for the bulk mixed micelles demonstrate a maximum at n = 12 for the C(n)TAB + SDS system. This correlation between properties of the surface and bulk micelles suggests that the mechanical properties of the surface micelles are largely determined by the interactions between surfactant molecules with surfactant-substrate interactions playing a secondary role.