Transitional Liquid Crystalline Phases between the Hexagonal and Lamellar Phases in Ternary Cesium N-Tetradecanoate-Water-Additive Mixtures

John C. Blackburn and Peter K. Kilpatrick

Department of Chemical Engineering, North Carolina State University, Raleigh, North Carolina 27695-7905

Available online 26 April 2002.

Abstract

The effects of added salt (CsOH, CsCl), long-chain carboxylic acid, and long-chain alcohol on the lyotropic liquid crystalline phase behavior in the cesium n-tetradecanoate (CsTD)-water system is reported. The transitional region between the hexagonal (H_a) and lamellar (L_a) phases was the compositional range of focus. Three transitional phases were observed: (i) the ribbon (R) phase, a biaxial phase consisting of cylinders of ellipsoidal cross section; (ii) the viscous isotropic (VI) phase, an isotropic phase thought to consist of interconnected rods on an 1a3d lattice; and (iii) the intermediate (Int) phase, a uniaxial anisotropic phase thought to consist of interconnected rods on a planar lattice. The effect of the additives was to decrease the "interfacial curvature" of the surfactant head group layer by varying head group repulsion and by varying the surfactant tail volume relative to the surfactant head group area. These changes resulted in formation of transitional phases seeming to possess curvature between that of the cylindrical H_a phase and the planar L_a phase. The ionic repulsion between carboxylate head groups was reduced by the addition of CsOH or CsCl, and resulted in destabilization of the VI phase and the formation of the anisotropic Int phase. With the addition of cosurfactants, n-tetradecanoic acid (TDA) and 1-tetradecanol (TDOH), no Int phase was observed. With 7 wt% added TDA the R phase was stabilized up to temperatures of 336 K, above the 330 K temperature limit in the binary CsTD-D₂O system. In all four systems, sufficient additive (5-10 wt%) resulted in a transition to the L_a phase, which was stable over a large portion of the compositional range. In order of apparently decreasing mean curvature, the phase sequence is: hexagonal, ribbon, viscous isotropic, intermediate, and lamellar. The inferred structures are remarkably similar to reports in sodium dodecyl sulfate- and alkyl trimethyl ammonium chloride-water binary systems, as well as to liquid crystal formation in block copolymer systems.