Effect of polydispersity and soft interactions on the nematic vs. smectic phase stability in platelet suspensions

TL;DR

This study uses density-functional theory to analyze how polydispersity and soft interactions influence the stability of nematic versus smectic phases in platelet suspensions, revealing how these factors affect phase transitions and stability.

Contribution

It provides a theoretical framework for understanding phase behavior in polydisperse platelet suspensions with soft interactions, extending previous models to include polydispersity and attractive/repulsive forces.

Findings

Polydispersity enhances smectic phase stability.

Purely hard interactions predict a continuous nematic-smectic transition.

Soft attractive forces can induce first-order transitions and nematic demixing.

Abstract

We discuss theoretically, using density-functional theory, the phase stability of nematic and smectic ordering in a suspension of platelets of the same thickness but with a high polydispersity in diameter, and study the influence of polydispersity on this stability. The platelets are assumed to interact like hard objects, but additional soft attractive and repulsive interactions, meant to represent the effect of depletion interactions are also considered. The aspect (diameter to thickness) ratio is taken to be very high, in order to model solutions of mineral platelets recently explored experimentally. In this regime a high degree of orientational ordering occurs; therefore the model platelets can be taken as completely parallel and are amenable to analysis via a fundamental-measure theory. Our focus is on the nematic vs. smectic phase interplay, since a high degree of polydispersity in diameter suppresses the formation of the columnar phase. When interactions are purely hard, the theory predicts a continuous nematic-to-smectic transition, regardless of the degree of diameter polydispersity. However, polydispersity enhances the stability of the smectic phase against the nematic phase. Predictions for the case where an additional soft interaction is added are obtained using mean-field perturbation theory. In the case of the one-component fluid, the transition remains continuous for repulsive forces, and the smectic phase becomes more stable as the range of the interaction is decreased. The opposite behaviour with respect to the range is observed for attractive forces, and in fact the transition becomes of first order below a tricritical point. Also, for attractive interactions, nematic demixing appears, with an associated critical point. When platelet polydispersity is introduced the tricritical temperature shifts to very high values.