Dynamics in dense hard-sphere colloidal suspensions

TL;DR

This study investigates the dynamic behavior of dense hard-sphere colloidal suspensions using advanced X-ray techniques, revealing the limitations of existing theories at high concentrations and validating some theoretical predictions with experimental data.

Contribution

The paper provides experimental validation and comparison of hydrodynamic functions and diffusion coefficients in dense colloids, highlighting discrepancies in existing theories at high concentrations.

Findings

Hydrodynamic interactions significantly slow particle mobility even at low concentrations.

Good agreement with many-body theory at moderate concentrations, discrepancies at high concentrations.

Validation of Mode Coupling Theory predictions for relaxation rates.

Abstract

The dynamic behavior of a hard-sphere colloidal suspension was studied by X-ray Photon Correlation Spectroscopy and Small Angle X-ray Scattering over a wide range of particle volume fractions. The short-time mobility of the particles was found to be smaller than that of free particles even at relatively low concentrations, showing the importance of indirect hydrodynamic interactions. Hydrodynamic functions were derived from the data and for moderate particle volume fractions (> 0.40) there is a good agreement with earlier many-body theory calculations by Beenakker and Mazur [C.W.J. Beenakker and P. Mazur, Physica A 120, 349 (1984)]. Important discrepancies appear at higher concentrations, above ~0.40, where the hydrodynamic effects are overestimated by the Beenakker-Mazur theory, but predicted accurately by an accelerated Stokesian dynamics algorithm developed by Banchio and Brady [A.J. Banchio and J. F. Brady, J. Chem. Phys. 118, 10323 (2003)]. For the relaxation rates, good agreement was also found between the experimental data and a scaling form predicted by Mode Coupling Theory. In the high concentration range, with the fluid suspensions approaching the glass transition, the long-time diffusion coefficient was compared with the short-time collective diffusion coefficient to verify a scaling relation previously proposed by Segre and Pusey [P.N. Segre and P.N. Pusey, Phys. Rev. Lett. 77, 771 (1996)]. We discuss our results in view of previous experimental attempts to validate this scaling law [L. Lurio et al., Phys. Rev. Lett. 84, 785 (2000)]