Effect of Solvent Quality on Aggregate Structures of Common Surfactants

Aggregate structures of two model surfactants, AOT and C12E5 arc studied in pure solvents D2O, dioxane-d(8) (d-diox) and cyclohexane-d(12) (C6D12) as well as in formulated D2O/d-diox and d-diOX/C6D12 mixtures. As such these solvents and mixtures span a wide and continuous range of polarities. Small-angle neutron scattering (SANS) has been employed to follow an evolution of the preferred aggregate curvature, from normal micelles in high polarity solvents, through to reversed micelles in low polarity media. SANS has also been used to elucidate the micellar size, shape as well as to highlight intermicellar interactions. The results shed new light on the nature of aggregation structures in intermediate polarity solvents, and point to a region of solvent quality (as characterized by Hildebrand Solubility Parameter, Snyder polarity parameter or dielectric constant) in which aggregation is not favored. Finally these observed trends in aggregation as a function of solvent quality are successfully used to predict the self-assembly behavior of C12E5 in a different solvent, hexane-d(14) (C6D14).