Quasi-anomalous diffusion processes in entangled solutions of wormlike surfactant micelles.
In this article, we present a detailed analysis of the dynamic properties of entangled solutions of semi-flexible, threadlike surfactant micelles. These aggregates were formed by self-association processes in aqueous solutions of cationic surfactants such as cetylpyridinium chloride (CPyCl) or cetyltrimethylammonium bromide (CTAB) after the addition of different amounts of sodium salicylate (NaSal). We performed dynamic light scattering (DLS) experiments in combination with rheological measurements in order to investigate the dynamic properties of these viscoelastic surfactant solutions. In all samples, we observed three distinct relaxation regimes: initial monoexponential decay, followed by a power-law behavior at intermediate observation times. A second monoexponential region was detected at very long times, and this terminal regime described the viscoelastic features of the samples. The fast decay mode was induced by local cooperative motions in the gellike network. The intermediate and slowest decay modes point to the existence of quasi-anomalous diffusion processes. These phenomena are characterized by linear-diffusion properties at long times, and they obeyed anomalous logarithmic slow-dynamics behavior at intermediate time zones. The anomalous diffusion properties at intermediate time scales can be induced by the bending motions of the rod-shaped micelles between two entanglement points. This regime, which was more extended at lower temperatures, was described by the power-law form of the correlation function. The power-law exponent depended on the chemical structure of the surfactants and the temperature. The power-law regime shifted toward earlier times as the gellike network evolved. The slowest mode of the correlation function coincided very well with the shear stress relaxation times of the three-dimensional, transient networks. We observed that the temperature dependence of the slowest mode followed Arrhenius laws. This result provides experimental evidence for thermally activated topological relaxation processes of random fluid phases. We obtained activation energies of approximately 30 kcal/mol, and these data coincided well with previously reported literature values, which were determined in similar surfactant solutions. Characteristic "screening lengths", over which viscous effects became important, could also be determined from the activation energy. The elastic modulus G0, calculated from the slowest mode of the correlation function, was in pretty good agreement with rheological data. The light-scattering spectra were consistent with the theoretical model of dynamical coupling of the concentration fluctuations to viscoelasticity. Since only minute sample volumes are required for advanced DLS experiments, this method to extract viscoelasticity is well suited for advanced studies of gellike biomaterials.
Lehrstuhl für Physikalische Chemie II, Universität Dortmund, Otto-Hahn-Strasse 6, D-44227 Dortmund, Germany.
Anuj
A
Shukla
Reiner
R
Fuchs
Heinz
H
Rehage