Transport properties of polydisperse hard sphere fluid: Effect of distribution shape and mass scaling

TL;DR

This paper develops analytical models to study how size distribution shape and mass scaling influence transport properties in concentrated polydisperse hard sphere fluids, with results validated against simulations.

Contribution

It introduces a simple analytical approach based on the Boltzmann equation for calculating transport coefficients in polydisperse systems considering distribution shape and mass scaling effects.

Findings

Transport coefficients are insensitive to distribution shape at low polydispersity.

Analytical results agree well with simulations for diffusion and thermal conductivity.

Shear viscosity predictions match simulations up to 20-40% polydispersity.

Abstract

A model polydisperse fluid represents many real fluids such as colloidal suspensions and polymer solutions. In this study, considering a concentrated size-polydisperse hard sphere fluid with size derived from two different distribution functions, namely, uniform and Gaussian and explore the effect of polydispersity and mass scaling on the transport properties in general. A simple analytical solution based on the Boltzmann transport equation is also presented (together with the solution using Chapman-Enskog (CE) method) using which various transport coefficients are obtained. The central idea of our approach is the realization that, in polydisperse system, the collision scattering cross section is proportional to a random variable \textit{z} which is equal to the sum of two random variables $\sigma_i$ and $\sigma_j$ (representing particle diameters), and the distribution of \textit{z} can be written as the convolution of the two distributions $P(\sigma_i)$ and $P(\sigma_j)$. The obtained transport coefficients are expressed as explicit function of polydispersity index, $\delta$, and their dependence on the nature of particle size distribution is explored. It is observed that in the low polydispersity limit, the transport coefficients are found to be insensitive to the type of size distribution functions considered. The analytical results (for diffusion coefficients and thermal conductivity) obtained using Chapman-Enskog method and our simple analytical approach agrees well with the simulation. However, for shear viscosity, our analyical approach agress for $\delta \le 20\%$, while it agrees upto $\delta \approx 40\%$ with the result obtained using CE-method (in the limit $\delta \rightarrow 0$). Interestingly, the effect of scaling mass (i.e., mass proportional to the particle size and thus a random variable) produces no significant qualitative difference.