Phase behavior of binary hard-sphere mixtures: Free volume theory including reservoir hard-core interactions

Abstract

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Phase stability of colloidal mixtures of spheres and rods

“…Free volume theory 13,40 is a versatile tool used for the prediction of the phase behaviour of colloidal systems interacting via depletion forces. Here we outline the FVT method used in this paper which is based on previous work on binary hardsphere mixtures 39 , but extended to take anisotropic shape of rod-like depletants into account.…”

“…Here we follow a FVT approach where the excluded volume of the rod-like depletants is explicitly accounted for, similar as was recently developed for binary hard-sphere mixtures 39 . Using this FVT method, Eq.…”

“…The experimental observations are compared with FVT results. To this end, we adjusted the original FVT approach to explicitly account for the excluded volume of the rod-like depletants in both the reservoir and the system, as done recently for hard sphere depletants by Opdam et al 39 . The effective excluded volume of rods with large aspect ratio is very large due to their anisotropic shape and we will show that incorporating this excluded volume in FVT significantly improves the theoretical predictions with respect to the experimental results.…”

Excluded volume interactions and phase stability in mixtures of hard spheres and hard rods

“…Here, we outline the FVT employed in this paper, which is based on previous work on binary HS mixtures 15 but extended to take the anisotropic shape of rod-like depletants into account. 27 In FVT the two compartments used are in osmotic equilibrium and the thermodynamic properties of the system can be described by the semi-grand potential Ω .…”

“…Opdam et al 15 improved the FVT approach by explicitly incorporating excluded volume interactions between the small HS depletants at all levels. The resulting FVT predictions were much closer to the computer simulations of Dijkstra et al 14 and also predicted the solid–solid phase equilibria.…”