Effect of thermal history on the morphology of thermotropic liquid crystalline copolyesters based on PET and PHB

Abstract Morphological studies were carried out on thermotropic liquid crystalline copolyesters based on poly(ethylene terephthalate) (PET) and para-hydroxybenzoic acid (PHB), where PHB content varied from 30 mole percent up to 80 mole percent. The technique of chemical etching, using n-propylamine as the etchant, coupled with scanning electron microscopy was utilized to obtain structural information. Scanning electron microscopy results on chemically etched, compression moulded films show that selective chemical etching of the PET rich regions occur. This indicates that the morphology of the copolymers is hetergeneous in nature. Further support regarding a hetergeneous morphology was obtained by transmission electron microscopy. A morphological model has been proposed based on these results. The observance of non-equilibrium behaviour associated with amorphous PET regions (as seen from d.s.c. measurements) also strongly indicates the presence of a phase rich in PET and thus supports the non-homogeneous morphological model. Thermal analysis of these copolyesters suggests that the chain structure is non-random and this is an agreement with results published by Wunderlich et al. The glass transition temperature typically associated with PET is present and remains constant in all copolymers compositions where PET is the continuous phase. Further, the melting temperatures obtained experimentally are higher than the values predicted by theory for random copolymers and the melting endotherms are relatively narrow. These observations also indicate a non-random chain structure. Structural studies conducted on films compression molded at different temperatures show that morphological rearrangement occurs at higher temperatures with the formation of domains of the order of 10 microns.