ABSTRACT
Herein, homogeneous solutions of cationic gemini surfactants, alkanediyl-α,ω-bis(dimethyldodecylammonium bromide), referred to as 12-s-12 where s = 2, 4, 6, 8, and 10, in cyclohexane have been prepared with the help of sodium hexanoate (SH) or sodium laurate (SL). These surfactants self-assembled in cyclohexane to form various aggregating structures, which were characterised by small-angle X-ray scattering (SAXS) together with polarised microscopy observations. The results showed that 12-2-12/SH, where the gemini had the shortest spacer among this series, formed an inverse micellar cubic liquid crystalline phase of the Fd3m structure. 12-s-12/SL, including s = 4, 6, and 8, which contained an adequate length spacer, formed an inverse hexagonal liquid crystalline phase packed by the cylindrical assemblies of surfactants. 12-10-12/SL, in which the gemini had a longer spacer, formed dispersed reverse vesicles (a lamellar structure). The rheological properties of liquid crystalline phases in a linear visco-elastic regime were studied. 12-2-12/SH formed a hard gel, whereas 12-s-12/SL formed soft gels. Dynamic light scattering and steady-state viscosity analyses were performed for the reverse vesicle solutions formed by 12-10-12/SL. In all these systems, the amount of added water W0, denoting the mole ratio of water to the gemini surfactant, was demonstrated to influence the properties.
ABSTRACT
The quaternary ammonium gemini surfactants 12-s-12 (s = 2, 6, and 10) can produce homogeneous cyclohexane solutions with the assistance of salts, sodium benzoate (NaBez), sodium salicylate (NaSal), or sodium 2-bromoethanesulphonate (NaBres). In these samples, 12-s-12/salt formed aggregates and their structures were assigned by SAXS measurements together with POM observations. Among the three salts, both NaBez and NaBres had similar effects on assisting aggregate formation, but NaSal favoured the generation of aggregates of 12-s-12 with lower interface curvature. For example, both 12-2-12/NaBez and 12-2-12/NaBres formed an I2 liquid crystalline (LC) phase with an Fm3m structure, but 12-2-12/NaSal generated a H2 LC phase. Both 12-6-12/NaBez and 12-6-12/NaBres generated a H2 LC phase, while 12-6-12/NaSal yielded both H2 and V2 phases with Pn3m symmetry, both of which co-existed in solution. The special effect of NaSal was attributed to its ortho-hydroxyl in the benzene ring. This favoured the formation of intermolecular hydrogen bonds among the NaSal molecules attracted to the quaternary ammonium head of 12-s-12. The water molecules joined between the NaSal molecules to build hydrogen-bonding bridges, which further increased the size of the 12-s-12 head. This benefited the formation of aggregates with lower surface curvature. In the systems of both NaBez and NaBres, the spacer length of the gemini surfactants dominated the morphology of the formed aggregates, wherein the effect of the salt was significantly weaker. Finally, the visco-elasticity of samples with similar aggregates was measured and the rheological behaviour discussed.
