Yoshinobu Nozue

Molecular Basis of the Shish-Kebab Morphology in Polymer Crystallization

In the rich and long-standing literature on the flow-induced formation of oriented precursors to polymer crystallization, it is often asserted that the longest, most extended chains are the dominant molecular species in the “shish” of the “shish-kebab” formation. We performed a critical examination of this widely held view, using deuterium labeling to distinguish different chain lengths within an overall distribution. Small-angle neutron-scattering patterns of the differently labeled materials showed that long chains are not overrepresented in the shish relative to their concentration in the material as a whole. We observed that the longest chains play a catalytic role, recruiting other chains adjacent to them into formation of the shish.

Spatial distribution of lamella structure in PCL/PVB band spherulite investigated with microbeam small- and wide-angle X-ray scattering

The microbeam small- and wide-angle X-ray scattering (SAXS/WAXS) technique gives the novel information about micron-scale structural inhomogeneity of polymer crystal. By using this technique, we have studied structural inhomogeneity of lamella within the band spherulite of miscible polymer blend poly(e caprolactone) (PCL)/poly(vinyl butyral) (PVB) and the structure development of lamella during crystallization. It is known that PCL/PVB forms very large spherulites (∼several mm in radius) with highly regular band structure because of low frequency of nucleation and that PCL/PVB crystallized at 41 °C has at least two kinds of lamella structure (150 A, 180 A). With an X-ray microbeam initially fixed outside near the growth front of the band spherulite, we have observed the lamella formation at the local point and have found that the larger long period grows before the appearance of the shorter long period. We have also observed that the orientation of lamella with the larger long period is different from that of lamella with the shorter long period from SAXS experiment with an X-ray microbeam scanning the band spherulite along its radial direction. Further, the discontinuity in lamella twisting was observed from scanning microbeam WAXS. Based on the experimental results, we propose two possible spatial distribution models. The result of PCL/PVB crystallized at 35 °C was also discussed.