Sedimentation stacking diagrams of binary mixtures of thick and thin hard rods

TL;DR

This study uses Onsager theory to analyze sedimentation-diffusion equilibrium in binary mixtures of thick and thin hard rods, revealing complex stacking sequences and cautioning against straightforward interpretation of bulk phase diagrams from sedimentation data.

Contribution

It introduces detailed stacking diagrams for binary rod mixtures and uncovers complex sedimentation sequences, highlighting the intricacies in relating sedimentation profiles to bulk phase behavior.

Findings

Sixteen distinct stacking sequences identified.

Counter-intuitive stacking sequences such as isotropic between nematic phases.

Sedimentation profiles can mislead bulk phase interpretations.

Abstract

We use Onsager theory and the local density approximation to study sedimentation-diffusion equilibrium density profiles of binary mixtures of thick and thin hard rods. We construct stacking diagrams for three diameter ratios, and find that even a simple spindle-shaped phase diagram with only isotropic-nematic demixing can lead to counter-intuitive stacking sequences such as an isotropic phase sandwiched between two nematic phases. For the most complex phase diagram considered here, we find sixteen distinct stacking sequences, including several with five sedimented layers. By adding sedimentation paths to composition-pressure and density-density phase diagrams and calculating density and composition profiles, we show that conclusions about bulk phase diagrams of binary mixtures on the basis of sedimentation-diffusion equilibria should be drawn warily.