Crossover behavior in micellar solutions with lower critical demixing point: broadband ultrasonic spectrometry of the isobutoxyethanol-water system.

The aggregation kinetics of isobutoxyethanol-water mixtures with lower critical demixing point has been investigated. Two types of kinetics have been observed, a diffusion-controlled formation of micellar species and the formation of a microheterogeneous liquid structure, governed by fluctuations in the local concentration. Ultrasonic attenuation spectra of isobutoxyethanol-water mixtures have been measured between 100 kHz and 2 GHz at 25 degrees C and at several concentrations, covering the complete composition range. With the mixture of critical composition measurements have been performed at some temperatures near the critical temperature (T(c)=299.51 K). In addition to the asymptotic high frequency background contribution, the broadband spectra reveal a Bhattacharjee-Ferrell relaxation term due to critical concentration fluctuations, a restricted Hill term reflecting the monomer exchange between micelles and the suspending phase, and two Debye-type relaxation terms that are assigned to chemical relaxations. The relaxation rates of the Bhattacharjee-Ferrell term exceed those from static and dynamic light scattering (amplitude Gamma(0)=5.3 x 10(9) s(-1)), likely due to the effect of a second parallel pathway of relaxation in the ultrasonic field. The adiabatic coupling constant following from the amplitude in the ultrasonic spectrum agrees with that from a thermodynamic relation (g=1.3). The restricted Hill term displays the features of an extended Teubner-Kahlweit-Aniansson-Wall model of the micelle formation and decay kinetics in surfactant solutions with high critical micelle concentration (C=0.6 mol/l). The idea of a fluctuation controlled monomer exchange in aqueous solutions of poly(ethylene glycol) monoalkyl ether-water mixtures near the critical point is briefly discussed.