Molecular structure and orientation in processed polymers: 2. Application to aromatic polyester fibers

Abstract

We characterize the orientation distribution function (ODF) of molecular-scale structure in a set of solution- and melt-spun fibers of a liquid crystalline polyester in order to assess the role of processing in these fibers. The polyester is composed of 40% 1,4-hydroxybenzoic acid, 30% isophthalic acid, and 30% hydroquinone. Crystallinity is measured by both wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). A three-component model, consisting of crystalline, oriented non-crystalline, and unoriented non-crystalline components, is required to describe completely the X-ray scattering properties of the fibers. Monte Carlo simulations are used to define the ensemble structure on the atomic scale, for which the resulting ODF is determined. Our results indicate that a single ensemble of dimers on a 3×3 rhombic lattice can be used to characterize the molecular-level non-crystalline structure in all the fibers considered. Fibers spun from the nematic melt produce samples with higher degrees of global orientation as well as a higher degree of crystallinity than those spun from solution. Our results also show that the mechanical bias of the fiber spinning process induces an initial degree of orientation which is then enhanced and perfected, especially in the directions lateral to the chain, by subsequent annealing.