Transport coefficients in glassy colloidal fluids

摘要

Our microscopic theory of entropic barrier formation and activated hopping for hard-sphere colloidal suspensions [K. S. Schweizer and E. J. Saltzman, J. Chem. Phys. 119, 1181 (2003), preceding paper] is combined with general statistical mechanical relations and a binary-collision-type model for the low-viscosity regime [E. G. D. Cohen, R. Verberg, and I. M. deSchepper, Physica A 251, 251 (1998)] to construct a theory for transport properties applicable for all particle concentrations. Quantitative, no adjustable parameter comparisons with experimental measurements of the self-diffusion constant and shear viscosity over a wide range of volume fractions show that the theory is quite accurate. The ability of model functions which contain dynamic singularities to describe our theoretical results is also established. Critical power laws and free-volume models can fit the theoretical calculations quite well over three to six orders of magnitude variation in the high-concentration regime, but all deviate qualitatively at sufficiently low and high volume fractions. (C) 2003 American Institute of Physics. [References: 29]