Spatio-orientationally organized polymer microstructures obtained on self-assembled pattern-forming states of liquid crystals: Morphology, phase separation, and potential applications

The main objective of the dissertation is to develop and exploit a novel technique for imparting multidimensional spatial and orientational order into polymer networks. This approach is based on the use of pattern-forming states of liquid crystals as templates for the network formation. To demonstrate the feasibility and flexibility of this concept, we describe various pattern-forming states observed from ordinary cholesteric and nematic/cholesteric dual-frequency liquid crystals. We present a variety of polymer microstuctures templated on those pattern-forming states. This clearly demonstrates the feasibility and flexibility of templating both orientational and positional order of host pattern-forming states into polymer network.; We investigated possible driving forces behind this templating effect of LC pattern-forming states. These include effects of both spatial variations of UV intensity and gradients in elastic distortion caused by the spatial modulation of director field. The effects of the two mechanisms are separated through a series of experiments, including polarization-selective photopolymerization, FTIR imaging of the monomer distribution prior to UV-exposure and initiation of the photoreaction, the effect of temperature on the templated morphology, and the use of a thermal reactive monomer to remove the effect of possible optical inhomogeneities. The model derives from the concept of director gradient templating, whereby monomer phase separation is driven by a competition between reduction in elastic energy when monomer replaces liquid crystal in more (or less) distorted regions of the molecular director, and a consequent decrease in the entropy of mixing of the two species.; Another emphasis of this dissertation is to study the control over the network morphology in the "third" dimension---perpendicular to UV wavefront---by relatively simple means of selecting the wavelength of UV light used in photopolymerization to be inside or outside a carefully characterized absorption band. The spatial variation in polymerization rate with consequent diffusion of monomer results in surface-localized networks.; The final objective is to demonstrate potential applications of LC pattern-forming states and their templating effect, including switchable phase gratings, orientational/positional pattern formation of functional materials (e.g., conducting polymers), and potentiality of this novel interaction for future research.