The crystallinity of poly(phenylene sulfide) and its effect on polymer properties



The crystallinity and crystallizability of poly(phenylene sulfide) have been examined by a number of common techniques. Several provided qualitative information, but only one, x-ray diffraction, was considered sufficiently reliable and reproducible to allow quantitative comparisons. Based on x-ray measurements, an approximate degree of crystallinity, termed crystallinity index (Ci), could be readily assigned. According to this method, virgin polymer possesses significant crystallinity (Ci ≈ 65%). Curing (crosslinking) the resin below its melting point did not change the crystallinity but did affect the crystallizability. Lightly cured resin suitable for molding and film extrusion was easily quenched from the melt to give amorphous polymer. The amorphous samples crystallized rapidly when heated to temperatures > 121°C (250°F). At mold temperatures below 93°C (200°F), moldings with very low surface crystallinity were produced. Annealing (204°C, 400°F) caused rapid crystallization of such moldings, and changes in crystallinity were correlated with observed changes in physical properties. The resin crystallizes so rapidly that these quenched moldings possessed a crystallinity gradient, the internal crystallinity being substantially greater. At high mold temperatures (121–204°C, 250–400°F), moldings very similar to fully annealed specimens were obtained.