Monomer functionality effects in the anisotropic phase separation of liquid crystals

Holographic gratings formed through the anisotropic phase separation of liquid crystals show promise as switchable optical elements. In order to form useful elements, however, it is necessary to control the nanoscale morphologies within the grating films. In this manuscript, we evaluate the role of monomer functionality on the morphology and the electro-optical properties of both gratings and conventional scattering polymer-dispersed liquid crystal (PDLC) films. Both of these structures are formed using polymerization-induced phase separation (PIPS) of liquid crystals from a cross-linked polymer formed through free-radical photo-polymerization. Floodlit (uniform illumination) films and holographic gratings (from non-uniform illumination caused by the interference of two laser beams) were made using monomers with 2-5 acrylate groups, while keeping the LC concentration constant in the syrups. The morphologies of these films were examined using low voltage scanning electron microscopy (LVSEM). In all cases, very small LC domains were formed with little indication of growth or coalescence. Lowering monomer functionality reduced the volume fraction of phase-separated domains in the floodlit samples. For the grating samples, the local volume fraction and the LC domain sizes decreased substantially as the monomer functionality was decreased. Using detailed image analysis, differences in the anisotropy of the domains was also probed. A much stronger tendency to form anisotropically-shaped domains was observed for the higher functional syrups. These domain anisotropy differences are correlated with the number of reactive double bonds per monomer and are suggestive of local environmental differences exerted at the time of the domain formation. (C) 1999 Elsevier Science Ltd. All rights reserved.