Influence of Spacer of Gemini on the Interactions between Cationic Gemini Surfactant and Stearic Acid in Mixed Monolayers

Mixed Langmuir-Blodgett (LB) films composed of a cationic gemini surfactant, [C18H37(CH3)(2)N+-(CH2)(s)-N+(CH3)(2)C18H37],2Br(-) (18-s-18 with s = 3, 6, 8, 10 and 12), and a fatty acid of stearic acid (SA) were studied by the pi-A isotherm measurement, as well as by AFM and FT-IR. The analysis of the mean molecular area, the excess area and the excess Gibbs free energy from pi-A isotherms suggests the existence of attractive interactions between 18-s-18 and SA molecules in the mixed monolayers. The spacer group of 18-s-18 plays a very important role in the surface properties of 18-s-18/SA mixed monolayers. When s <= 8, 18-s-18 and SA are completely miscible, while partially miscible mixed monolayers are presented when s > 8. Especially, in the latter case, when s = 12, phase separation appears in two composition regions of X-SA = 0.4-0.75 and X-SA = 0.75-0.85, respectively. This miscible phenomenon is confirmed by AFM observation. The result of FT-IR indicates that when X-SA <= 0.67, SA could ionize completely and form a "cationic-anionic surfactant" with 18-s-18 owing to the electrostatic interaction between the head groups, while when X-SA > 0.67, SA only partially ionizes, -COO- and -COOH coexist in mixed monolayers.