Composition and temperature effects on the solution structure of SDS/octanol/brine by SANS, NMR and microscopy

Abstract

We investigate the solution structures of model sodium dodecyl sulfate/octanol/brine ternary mixtures across the lamellar (L_α), vesicle (L₄) and micellar (L₁) phases employing small angle neutron scattering (SANS), optical microscopy and nuclear magnetic resonance (NMR). Specifically, we examine the effect of co-surfactant octanol (0.2–9.48 w/v%) and temperature (25–65 °C) along dilution lines at fixed octanol : SDS ratios (0.08–1.21). A transition from L_α to sponge phase (L₃) above 35 °C is found along the octanol : SDS = 1.21 isopleth, with phase coexistence above ϕ ≈ 0.14 weight fraction of surfactant and co-surfactant. The lamellar bilayers swell upon dilution, with an approximately linear increase of d-spacing, accompanied by a decrease of the Caillé parameter, indicative of greater membrane rigidity. At a lower octanol : SDS ratio of 0.62, coexistence of oblate micelles and vesicles is observed with preferential formation of vesicles at low concentrations. Dilution of the L₁ phase, along octanol : SDS = 0.08, results in elongated micelles, as the NaCl : SDS ratio increases, while higher temperatures favour the formation of less elongated micelles. Our results provide a detailed map of the equilibrium structures found in the L_α vicinity of this extensively investigated flow-responsive surfactant system.