Contrast Variation SANS Investigation of Composition Distributions in Mixed Surfactant Micelles

Abstract

Small angle neutron scattering measurements have been performed on three systems (HFDeP-d5-C (N-1(1,1,2,2-tetrahydroperfluorodecanoyl)pyridinium-d5 chloride)/C16PC in 63 mM NaCl; HFDeP-d5-C/C12PC in 200 mM NaCl, and as an example of an ideally mixed system, SDS/SDS-d25 in 200 mM NaCl) containing micelles formed in a binary mixture of surfactants, in order to investigate the composition distribution of the mixed micelles. The experimental data were collected varying the contrast between the average scattering length density of micelles and aqueous solvent by changing the H2O/D2O ratio. Analysis of data includes a modelindependent approachsthe indirect Fourier transformation method and direct modelingssimultaneous fit at all contrasts by the scattering from micelles of equal size and shape with composition distribution and an effective interaction. It has earlier been shown (Almgren, M.; Garamus, V. M. J. Phys. Chem. B 2005, 109, 11348) that for micelles of equal size, independent of the composition, and with negligible intermicellar interactions, the scattered intensity at zero angle varies quadratically with the contrast, with the minimum intensity at the nominal match point proportional to ó2, the variance of the micelle composition distribution. Within the regular solution framework, the composition distribution and its variance are uniquely defined by the value of the interaction parameter and the micelle aggregation number. At 25 °C, the first system gave ó ) 0.37, corresponding to a broad, bimodal composition distribution, the second ó ) 0.22, a broad distribution with a shallow minimum at the midpoint. For SDS/SDS-d25, we found ó ) 0.006 ( 0.030, which is a smaller value than that of the binominal composition distribution expected for an ideally mixed system.