Self-Assembly of Polyion–Surfactant Ion Complex Salts in Mixtures with Water and n-Alcohols

[Image: see text] Phase behavior and structural features were investigated for “complex salts”, consisting of the cationic hexadecyltrimethylammonium (CTA) surfactant with polyacrylate (PA(n), n = 30 or 6000) counterions, mixed with water and different n-alcohols (ethanol, butanol, hexanol, octanol, and decanol). The liquid crystalline structures formed were identified by small-angle X-ray scattering measurements, which provided information about the changes in the geometry of the aggregates as functions of the concentration and chain length of the added n-alcohol. The obtained results were compared with a previous work on similar ternary mixtures of the same cationic surfactant but with the monomeric bromide counterion, CTABr (Fontell, K.; Khan, A.; Lindström, B.; Maciejewska, D.; Puang-Ngern, S. Colloid Polym. Sci., 1991, 269, 727). In general, the same phases were detected in systems with the complex salts CTAPA(n) as in systems with CTABr, but the swelling of the various liquid crystalline phases by water was much more limited in the complex salt systems. An isotropic alcoholic phase was observed with all alcohols and the size of this region of the phase diagram increased for the shorter alcohols, except for ethanol. For mixtures with octanol and ethanol, in particular, the extensions of the disordered isotropic phases were larger for the complex salt with the shorter polyacrylate ions.