Nonionic Micelles near the Critical Point: Micellar Growth and Attractive Interaction

Abstract

We report on a series of SANS experiments on the structure of binary water−nonionic surfactant systems accompanied by complementary ultralow shear experiments and depolarized light scattering. The analysis gives a clear picture of the temperature dependence of aqueous solutions of nonionic surfactants of the n-alkyl polyglycol ether type (CiEj) when approaching the cloud point curve. The series is based on temperature variations from 3 °C up to a temperature of about 1.5 K below the critical point Tc and concentration variations around the critical concentration cc by a factor of 3−9. Six different surfactants were studied, changing the alkyl chain length i as well as the number of ethylene oxide groups j. Excluded volume effects were taken into account in the evaluation procedure by a generalized indirect Fourier transformation procedure recently developed for the evaluation of scattering data from semidilute and dense systems. The bottom line is that all systems examined show a sphere-to-rod transition, the degree of growth and the transition temperature depending on the concentration and hydrophobicity of the surfactant. Superimposed on this transition is the onset of attractive interactions as the cloud point curve is approached, the range depending on the overall surfactant size.