Phase behavior of polymer dispersed liquid crystals, comparison between mean-field theory, and coarse-grained molecular dynamics simulations

We report a simulation methodology to quantitatively predict the thermodynamic behaviour (phase diagrams) of polymer mixtures, that exhibit phases with broken orientational symmetry. Our system consists of a binary mixture of short oligomers (NA = 4) and long rod-like mesogens (NB = 8). Using coarse-grained molecular dynamics (CGMD) simulations we infer the topology of the temperature-dependent free energy landscape, from the probability distributions of the components for a range of compositions. The mixture exhibits nematic (N) and smectic phases (Sm-A) as a function of two temperature scales, Tc, that governs the demixing transition, and TNI the nematic–isotropic temperature. Thus in addition to the isotropic (I), a nematic (N) phases observed in simulations of similar systems earlier we report the formation of a new entropy-stabilized phase separated smectic-A (Sm-A) phase with alternating mesogen-rich and oligomer-rich layers. Using the mean-field free energy for polymer-dispersed liquid crystals (PDLCs), with suitably chosen parameter values, we construct a mean-field phase diagram that matches those obtained from CGMD simulations. Our results are applicable to mixtures of synthetic and biological macromolecules that undergo phase separation and are orientable, thereby giving rise to the liquid crystalline phases. Our proposed methodology has a distinct advantage over other computational techniques in its applicability to systems with complex molecular interactions and in capturing the coarsening dynamics of systems involving multiple order parameters.