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.

Characteristic cylindrical structures formed by ABC star-shaped terpolymers were investigated by microbeam small-angle X-ray scattering (SAXS) in addition to transmission electron microscopy (TEM). The polymer samples are composed of polyisoprene (I), polystyrene (S), and poly(2-vinylpyridine) (P); their volume ratios for I:S:P are 1:1:X, where X equals 0.7, 1.2, 1.3, and 1.9. The spotlike diffraction patterns were observed by microbeam SAXS due to scattering from a small number of ordered grains in the polymer samples, where the exact packing manners of the cylinders, or their lattice constants, have been clarified. In short, it has been found that the cross-sectional patterns of these tilings have the features of four Archimedean tiling patterns, i.e., (6.6.6), (4.8.8), (3.3.4.3.4), and (4.6.12). All the four SAXS patterns are quite consistent with the structural observation by TEM with regard to the crystallographic data.