Thermodynamics, Transition Dynamics, and Texturing in Polymer-Dispersed Liquid Crystals with Mesogens Exhibiting a Direct Isotropic/Smectic-A Transition

Experimental and modeling/simulation studies of phase equilibrium and growth morphologies of novel polymer-dispersed liquid crystal (PDLC) mixtures of PS (polystyrene) and liquid crystals that exhibit a direct isotropic/smectic-A (lamellar) mesophase transition were performed for PS/10CB (decyl-cyanobiphenyl) and PS/12CB (dodecyl-cyanobiphenyl). Partial phase diagrams were determined using polarized optical microscopy (POM) and differential scanning calorimetry (DSC) for different compositions of both materials, determining both phase separation (liquid/liquid demixing) and phase ordering (isotropic/smectic-A transition) temperatures. The Flory−Huggins theory of isotropic mixing and Maier−Saupe−McMillan theory for smectic-A liquid crystalline ordering were used to computationally determine phase diagrams for both systems, showing good agreement with the experimental results. In addition to thermodynamic observations, growth morphology relations were found depending on phase transition sequence, quench rate, and material composition. Three stages of liquid-crystal-rich domain growth morphology were observed: spherical macroscale domain growth (“stage I”), highly anisotropic domain growth (“stage II”), and submicrometer spheroid domain growth (“stage III”). Nanoscale structure of spheroidal and spherocylindrical morphologies were then determined via two-dimensional simulation of a high-order Landau−de Gennes model. Morphologies observed during stage II growth are typical of direct isotropic/smectic-A phase transitions, such as highly anisotropic “batonnets” and filaments. These morphologies, which are found to be persistent in direct isotropic/smectic-A PDLCs, could provide new functionality and applications for these functional materials.