Rubbed films of isomeric poly(4-vinylpyridine) and poly(2-vinylpyridine): surface morphology, molecular orientation, and liquid crystal alignability

Films of poly(4-vinylpyridine) (P4VP) and poly(2-vinylpyridine) (P2VP) were characterized before and after they were rubbed with a rayon velvet, and their liquid crystal (LC) aligning abilities were investigated. Atomic force microscopy images showed that microgrooves developed along the rubbing direction in the surfaces of the rubbed films of both polymers. Retardation and linearly polarized infrared spectroscopy analyses revealed that in both polymers the vinyl backbones are oriented along the rubbing direction, while the pyridine side groups are oriented perpendicular to the rubbing direction; the para-directions of the pyridine rings in the P4VP film have a tilt angle of about 45° in the plane perpendicular to the rubbing direction but the para-directions of the pyridine rings in the P2VP film align nearly in the film surface. These rubbed films were found to induce uniform, homogeneous LC alignment along the rubbing direction. Both LC alignments were, however, found to have low anchoring energies that are due to the inherently weak interactions of the LCs with the film surfaces. Moreover, LC cells prepared using these films were found to have only limited stability. These results lead to the conclusion that the microgrooves generated along the rubbing direction play a critical role in governing the alignment of LCs that weakly interact with the parallel oriented vinyl main chains in competition with the perpendicularly oriented pyridine side groups, despite their dimensions, which are larger than the LC molecules and thus limit their effectiveness. In addition, the zero degree pre-tilting behavior of the LCs on these films was investigated in detail, taking into account both the rubbing-induced orientations of the polymer segments and their anisotropic interactions with the LC molecules.