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The relationship among processing parameters, molecular orientation, and modulus of a thermotropic liquid crystalline copolyester synthesized from poly(ethylene terephthalate) and 60 mol.-% p-hydroxybenzoic acid was systematically investigated so that the dominant processing factors to result in high orientation and high modulus were elucidated. Solid filaments were prepared by shear flow in capillaries and elongational flow by spinning from the liquid crystalline phase of the copolyester at various processing conditions. Superstructure, especially molecular orientation, of the filaments was analyzed by wide angle X-ray scattering (WAXS), scanning electron microscopy (SEM), and polarizing optical microscope (POM). Also, tensile modulus of the filaments was determined. Although filaments prepared by means of shear flow in capillaries had the Hermans orientation function of about 0.3, tensile modulus and morphology by SEM and POM did not exhibit the evidence of high orientation of the filaments even at high ratios of length over diameter and high shear rates. In the elongational flow by spinning, the dominant processing parameters for molecular orientation and increasing of tensile modulus are a spin-draw ratio and an initial diameter of the filament. The small diameter results in high orientation and high modulus. Enhancement of modulus was independent of the processing conditions related to a relaxation process of molecular orientation, such as spinning temperature, strain rate, and cooling. These results imply that there exists a size effect for the orientation process.

Molecular Orientation and Modulus of a Thermotropic Liquid Crystalline Copolyester