MIXING AND PHASE SEPARATION IN LIQUID CRYSTAL/MATRIX SYSTEMS

Abstract

We review mixing and phase separation (demixing) in mixtures of low molecular weight liquid crystals (LCs) and organic matrices, with emphasis on aspects relevant to the formation of polymer-dispersed liquid crystal films. These films, which contain a myriad of micron-sized LC droplets, are of interest because of their electro-optic properties. Film formation is simple: A liquid crystal and a liquid polymer precursor are initially mixed to form a single phase. Subsequently the polymer is hardened, and LC microdroplets phase-separate from the matrix. Although matrix hardening can be achieved in several ways, this review focuses on curing, during which cross-linking reactions lead to an increased matrix molecular weight. Topics discussed include: phase behavior of the binary system before, during, and after cure and LC/matrix solubilities. The Flory-Huggins model for phase separation (as modified by several workers) has provided a theoretical basis for the studies. Principal experimental tools have been calorimetry and light scattering. Uncured LC/matrix binaries possess phase diagrams with an upper critical solution temperature. Such systems, when heated through the mixing temperature, exhibit a decrease in specific heat, the (negative) excess specific heat of mixing, ∆ C mix . A plot of ∆ C mix vs. LC concentration exhibits a minimum, from which we can estimate LC and uncured-matrix solubilities. Matrix cure plays a major role in the phase separation process: In partially-cured samples, ∆ C mix transitions persist until cure is nearly complete, at which time a fraction of the LC is permanently phase-separated, with the rest remaining dissolved in the matrix. The kinetics of phase separation can be determined by calorimetry or light scattering. Cure rates have been shown to control LC microdroplet size, with fast cures leading to small droplets. Calorimetry of the fully cured system also allows us to determine the solubility of liquid crystal in the polymer matrix, as well as the fraction of phase-separated LC. An approximation based on the lever rule and the Flory-Huggins spinodal curve provides an upper bound for the solubilities and also describes their temperature dependence.