A POLARIZED INFRARED SPECTROSCOPIC STUDY OF MECHANICALLY INDUCED ORIENTATION IN SIDE-CHAIN LIQUID-CRYSTALLINE POLYMERS

We exploit the utility of infra-red dichroism for studying the orientation in thin films of side-chain liquid crystalline polymers (LCPs). Mechanical stretching of these polymers is difficult to perform because of difficulties in preparing the actual film samples necessary for the experiments. The method we used in this study consists of casting a thin LCP film onto the surface of a supporting conventional polymer film which can easily be prepared and stretched over a wide temperature range. Three nematic polyacrylates were investigated in this way, using poly(vinyl alcohol) as the supporting polymer. It is shown that stretching of the LCP film is sustained by extension of the supporting film and, similar to cross-linked nematic elastomers, an order parameter of approximately 0.4 for the mesogenic groups, determined by infra-red dichroism measurements, is obtained at a draw ratio as small as 1.5, i.e. only 50% deformation, indicating a rapid macroscopic alignment of the nematic domains along the mechanical field direction. Comparisons show that the mechanical stretching is particularly efficient for obtaining high orientation in side-chain LCPs having a short flexible spacer, the orientation of which is difficult to develop in a magnetic field, revealing an opposite influence of the length of the flexible spacer on the alignment of the nematic domains in both magnetic and mechanical fields. The mechanism of the orientation process in this stretching method is also examined. It is proposed that the stress field is essentially transferred to the nematic polymer through the interface between the nematic and supporting films, and that the alignment of the nematic domains, which starts in the interfacial region, could propagate throughout the sample by virtue of a strong cooperative movement among the nematic domains. The efficiency of the alignment propagation is higher for LCPs containing a short flexible spacer because of the stronger couplings between the chain backbone and the mesogenic groups.