Model experiments for a molecular understanding of polymer crystallization

Time-resolved real-space observations of morphology and pattern formation resulting from crystallization of ultrathin films of low-molecular-weight poly(ethylene oxide) (PEO) or diblock copolymers containing PEO shed light on the mechanisms of how polymer crystals are formed. We used simple but restricted geometries like thin films of controlled thickness or confinement resulting from block copolymer mesotructures. Under such conditions, we were able to relate the observed morphology and its temporal evolution directly to molecular processes and the kinetics of crystal growth. We demonstrate that changes in the morphology with time are due to different thermal histories and are the consequence of the mestable nature of polymer crystals. Information about the nucleation process was obtained by examining crystal for-mation in 12-nm small spherical cells of a block copolymer mesostructure. We discuss the advantages of thin-film studies for a better understanding of polymer crystallization. (C) 2003 Wiley Periodicals, Inc.