Effect of polydispersity on the evolution of density fluctuations to lamellar crystals in linear polyethylene

Abstract

The effect of polydispersity on structure development in linear polyethylenes is studied by simultaneous real time small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS). Our measurements show that below 128 °C, changes in the SAXS and WAXS intensity profiles for a broad molecular-weight distribution sample occur simultaneously as previously reported for a narrow molecular-weight distribution sample. We demonstrate that variations in the SAXS profile can be correlated with the morphological changes associated with the evolution of single chain folded crystal lamellae to lamellar aggregates. At 128 °C and higher temperatures, changes in the SAXS intensity profile for the broad molecular weight distribution sample occur much earlier than the onset of lamellar crystal growth evidenced in the WAXS profile. For the period before crystal growth is manifest in the WAXS scattering, the SAXS intensity at low angles increases while the domain size remains constant. The low-angle intensity uptake in SAXS can be best described by the Guinier approximation. On the other hand, the temperature dependence of the variation in the average crystal thickness during isothermal crystal growth is a function of the relative rates of primary crystallization and thickening at a given temperature. We discuss the effect of a broad distribution in chain length on the various stages in the development of the morphology.