Multiphase Coexistences in Rod–Polymer Mixtures

[Image: see text] Using recently derived analytical equations of state for hard rod dispersions, we predict the phase behavior of athermal rod–polymer mixtures with free volume theory. The rods are modeled as hard spherocylinders, while the nonadsorbing polymer chains are described as penetrable hard spheres. It is demonstrated that all of the different types of phase states that are stable for pure colloidal rod dispersions can coexist with any combination of these phases if polymers are added, depending on the concentrations, rod aspect ratio, and polymer–rod size ratio. This includes novel two-, three-, and four-phase coexistences and isostructural coexistences between dilute and concentrated phases of the same kind, even for the more ordered (liquid) crystal phases. This work provides insight into the conditions at which particular multiphase coexistences are expected for well-defined model colloidal rod–polymer mixtures. We provide a quantitative map detailing the various types of isostructural coexistences, which confirms an early qualitative hypothesis by Bolhuis et al. (J. Chem. Phys.107, 19971551).