Precursors of primary nucleation induced by flow in isotactic polypropylene

Small-angle X-ray scattering (SAXS) patterns of the sheared isotactic polypropylene (i-PP) melt at 175°C, above the nominal melting point of 162°C, showed development of oriented structures or aggregates of polymer molecules that did not disappear even after a long time relaxation (up to 2 h). However, the corresponding wide-angle X-ray diffraction (WAXD) patterns did not show any visible Bragg reflections, suggesting that the induced structures are probably non-crystalline. The results suggest that metastable aggregates of polymer molecules are generated in the melt by assembly of bundle of oriented chain segments (especially in long chains). We speculate that the oriented aggregates of chain segments are precursors of primary nuclei. The spatial arrangement of these precursors showed a layer-like superstructure, evident by the appearance of the meridional maxima in SAXS. The spacing between the 'layers' was estimated to be 430 Å. A microstructural model of the orientation-induced precursors for primary nucleation is presented. An Avrami model was used to fit the evolution of the oriented structures in i-PP melt, which provided insights into the early stages of polymer crystallization.