Polymeric Nematics of Associating Rods: Phase Behavior, Chiral Propagation, and Elasticity

Abstract

Rod-shaped colloids with attractive tips can form linear aggregates that may subsequently undergo hierarchical self-assembly into nematic fluids. Inspired by recent modelling efforts on chromonic liquid crystals, composed of discotic building blocks, we formulate a second-virial theory for reversible supramolecular rods. Unlike chromonics, these systems are capable of forming stable nematic phases in the high-temperature, monomeric limit in the absence of polymerization. Changing the tip potential from attractive to repulsive thus enables a smooth crossover from a monomeric to a polymeric nematic fluid. We analyze the isotropic-nematic phase behavior for both regimes and address the nematic elastic properties. The theory accounts for the molecular flexibility and chirality of the filaments and respects the intrinsic chain-length dependence of nematic order. We also discuss the impact of polymerization inhibitors on the phase behavior in the polymeric regime and find that the inhibitors cause a marked narrowing of the isotropic-nematic biphasic region, and generate reentrance nematization as well as a mass density inversion of the coexisting phases. We finally discuss the elastic moduli of rod-based polymeric nematics by qualitative comparing their elastic anisotropies with those of chromonic liquid crystals and other nanoparticle-based nematics.