Crystallization in diblock copolymer thin films at different degrees of supercooling.

The crystalline structures in thin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low and intermediate degrees of supercooling, but of submicrometer size for strong supercooling. Using grazing-incidence wide-angle x-ray scattering, we could determine the grain orientation distribution function which shows that the chain stems are perpendicular to the lamellae at low supercooling, but tilted at intermediate and strong supercooling. These results suggest that, at intermediate and strong supercooling, the crystalline PEO lamellae do not grow homogeneously, but by the formation of small crystallites at the growth front.

Morphological instabilities of polymer crystals.

We present experimental observations at comparatively low supercooling of morphology transitions from dendritic to faceted structures in polymer crystals growing in thin films of a poly-2-vinylpyridine-block-polyethyleneoxid copolymer. Our results are compared with theoretical concepts describing morphological instabilities of single crystals. Although these concepts originally were not developed for polymers, they allow to describe and interpret our experimental results quite well. In particular, the measured temperature dependence of the width W and frequency of dendritic side branches and the radius of curvature p of the growth tips of the crystals follow these concepts. We present preliminary evidence for the influence of polymer attachment kinetics and reorganisation processes behind the growth front. Polymer thin films provide valuable model systems for studying general concepts of crystallisation and allow to distinguish at which point the connectivity of the crystallising units within chain-like molecules starts to play a measurable role.