The dynamical crossover in attractive colloidal systems

Abstract

We study the dynamical arrest in an adhesive hard-sphere colloidal system. We examine a micellar suspension of the Pluronic-L64 surfactant in the temperature (T) and volume fraction (φ) phase diagram. According to mode-coupling theory (MCT), this system is characterized by a cusp-like singularity and two glassy phases: an attractive glass (AG) phase and a repulsive glass (RG) phase. The T - φ phase diagram of this system as confirmed by a previous series of scattering data also exhibits a Percolation Threshold (PT) line, a reentrant behavior (AG-liquid-RG), and a glass-to-glass transition. The AG phase can be generated out of the liquid phase by using T and φ as control parameters. We utilize viscosity and nuclear magnetic resonance (NMR) techniques. NMR data confirm all the characteristic properties of the colloidal system phase diagram and give evidence of the onset of a fractal-like percolating structure at a precise threshold. The MCT scaling laws used to study the shear viscosity as a function of φ and T show in both cases a fragile-to-strong liquid glass-forming dynamic crossover (FSC) located near the percolation threshold where the clustering process is fully developed. These results suggest a larger thermodynamic generality for this phenomenon, which is usually studied only as a function of the temperature. We also find that the critical values of the control parameters, coincident with the PT line, define the locus of the FSC. In the region between the FSC and the glass transition lines the system dynamics are dominated by clustering effects. We thus demonstrate that it is possible, using the conceptual framework provided by extended mode-coupling theory, to describe the way a system approaches dynamic arrest, taking into account both cage and hopping effects.