Morphological Transition in Fatty Acid Self-Assemblies: A Process Driven by the Interplay between the Chain-Melting and Surface-Melting Process of the Hydrogen Bonds

In surfactant systems, the major role of the nature of the counterion in the surfactant behavior is well-known. However, the effect of the molar ratio between the surfactant and its counterion is less explored in the literature. We investigated the effect of the molar ratio (R) between 12-hydroxystearic acid (12-HSA) and various alkanolamines as a function of the temperature in aqueous solution from the molecular scale to the mesoscale. By coupling microscopy techniques and small-angle neutron scattering, we showed that 12-HSA self-assembled into multilamellar tubes and transitioned into micelles at a precise temperature. This temperature transition depended on both the molar ratio and the alkyl chain length of the counterion and could be precisely tuned from 20 to 75 degrees C. This thermal behavior was investigated by differential scanning calorimetry and wide-angle X-ray scattering. We highlighted that the transition at the supramolecular scale between tubes and micelles came from two different mechanisms at the molecular scale as a function of the molar ratio. At low R, with an excess of counterion, the transition came from the chain-melting phenomenon. At high R, with an excess of 12-HSA, the transition came from both the chain-melting process and the surface-melting process of the hydrogen bonds. At the mesoscale, this transition of supramolecular assemblies from tubes to micelles delimited a regime of high bulk viscosity, with a regime of low viscosity.