Langmuir, Vol.23, No.12, 6554-6560, 2007
Ion exchange in catanionic mixtures: From ion pair amphiphiles to surfactant mixtures
We have studied concentrated equimolar mixtures of tetradecanoic acid (myristic acid, C13COOH) and hexadecyltrimethylammonium hydroxide (CTAOH) in which the OH- counterions are gradually exchanged by other anions (Cl-, Br-, CH3COO-, CH3-(C6H4)-SO3-). We demonstrate that the stability of a L-beta phase can be achieved at equimolarity between both surfactants, provided that the phase contains also a sufficient number of anions exchanged with OH-. In the absence of exchange (equimolar mixture of C13COOH and CTAOH), a three-dimensional crystalline L-c phase is produced. As the OH- ions are replaced by other ions, a swollen L-beta lamellar phase appears, first in coexistence with the L-c (D* = 400 angstrom) and then in coexistence with a dilute phase only (D* = 215 angstrom). In the latter regime, the repeating distance depends very little on the exchange ratio, but rather on the nature of the counterion. If too many OH- ions are exchanged, the L-beta phase becomes unstable again. A Poisson-Boltzmann model with charge regulation computed for a closed system predicts qualitatively the existence of this narrow domain of stability for the L-beta phase.