A metal-ligand coordinated surfactant system formed by calcium dodecylsulfate(Ca(DS)2)/tetradecyldimethylamine oxide (C14DMAO)/H2O was studied in terms of surface tension,conductivity,negative-staining TEM,phase behavior and rheological operation.In C14DMAO solution,when Ca(DS)2 is added,metal-ligand complexes form between the Ca 2+and N→O group of C14DMAO.Under this metal-ligand driving force,different phases can be obtained at different concentrations and different ratios of Ca(DS)2 and C14DMAO.At the fixed C14DMAO concentration,L1-phase consisting of spherical micelles forms at first.With the addition of Ca(DS)2,the spherical micelles elongate to be wormlike micelles and then after an L1/L-two phase region,the birefringent vesicle-phase(Lv-phase)region is observed.When Ca(DS)2 concentration continues to increase,a gel-phase region is found after the Lv-phase region and then precipitates of undissolved Ca(DS)2 appear.The transition between different phases is affected by temperature remarkably.The wormlike micellar solutions and vesicle solutions were checked by rheological measurements and showed apparent viscoelasticity at high surfactant concentrations.
Cationic base surfactant, tetradecyltrimethylammonium hydroxide (TTAOH), can be obtained through anion exchange from tetradecyltrimethylammonium bromide (TTABr). Salt-free cationic and anionic (catanionic) surfactant mixtures were studied by mixing TTAOH with oleic acid (OA) or stearic acid (SA) in water. The phase behavior of TTAOH/OA/H2O is compared with that of TTAOH/SA/H2O. It was found that the phase behavior of TTAOH/OA/H2O and TTAOH/SA/H2O system differs from each other due to the existence of the unsaturated double carbon bond (C=C) in OA. At fixed total surfactant concentration (25 mg/mL) of TTAOH/OA/H2O system at 25℃, one can observe an isotropic L1 phase, and a L1/Lα two-phase region with increasing OA content. The volume of top turbid Lα phase increases while the bottom phase changes gradually from transparently clear to a bit turbid until a single Lα-phase is reached. Finally at high OA concentration, excess OA is separated from the bulk aqueous solutions. TTAOH/SA/H2O system usually forms white precipitating at 25℃ due to the high chain melting temperature of SA. When heated to 60℃, however, the state of samples changes. At fixed total surfactant concentration of 25 mg/mL, an isotropic L1 phase and a milk-white or bluish Lα-phase are observed with increasing SA concentration. Transparent thin layers which are strongly birefringent form at the tops of some samples within the Lα-phase region. Finally, at high SA concentration, excess SA is separated from the bulk aqueous solutions. In addition to phase behavior study, we also measured the conductivity of TTAOH/OA/H2O system at 25℃ and TTAOH/SA/H2O system at 60℃, respectively. Surface tension and rheological measurements were also performed on typical samples.
