Analysis of structure and properties of poly(ethylene terephthalate) fibers

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Abstract
The structure of four semicrystalline poly(ethylene terephthalate) fibers were analyzed with full‐pattern (two‐dimensional Rietveld) x‐ray diffraction refinement, small‐angle x‐ray scattering, and thermal mechanical analysis, and compared to some of their known mechanical properties. The classical two‐phase model of crystal and amorphous phases were unable to correlate structure and properties. We found that there must be a third phase, an oriented, intermediate phase, located mainly between the fibrils. About 1/3 of the intensity of fiber diffraction of the analyzed samples was contributed from such intermediate phase. For some fiber properties the intermediate phase plays a similar role as proposed for “taut tie molecules.” A simple model for the description of structure‐insensitive properties of PET fibers was developed, based on this quantitaitve separation into three phases. The oriented intermediate phase changes the definition and calculation of the basic parameters of the fiber structure, such as crystallinity and orientation. Based on small‐angle x‐ray evidence, the crystallites are assumed to be separated by layers of largely amorphous material, both surrounded by the intermediate phase. The initial modulus of the fiber is determined mainly by the amount and orientation of the intermediate phase which has a maximum modulus of about 500 g/d on full orientation instead of the earlier predicted 150 g/d for fully oriented semicrystalline fibers. Based on the relationship between tenactity and average orientation function, the maximum tenacity for PET fibers of a structure like the ones analyzed may reach 20–45 g/d instead of earlier predictions of 10 g/d. The additional information needed to understand the structure‐sensitive property of shrinkage is discussed. Presently easily accessible parameters have no quantitative predictive capabilities. © 1994 John Wiley & Sons, Inc.