In general, when a crystal is molten, all molecules forget about their mutual correlations and long-range order is lost. Thus, a regrown crystal does not inherit any features from an initially present crystal. Such is true for materials exhibiting a well-defined melting point. However, polymer crystallites have a wide range of melting temperatures, enabling paradoxical phenomena such as the coexistence of melting and crystallization. Here, we report a self-seeding technique that enables the generation of arrays of orientation-correlated polymer crystals of uniform size and shape ('clones') with their orientation inherited from an initial single crystal. Moreover, the number density and locations of these cloned crystals can to some extent be predetermined through the thermal history of the starting crystal. We attribute this unique behaviour of polymers to the coexistence of variable fold lengths in metastable crystalline lamellae, typical for ordering of complex chain-like molecules.
Isothermal crystallization of the poly(ferrocenyl dimethylsilane) (PFDMS) segments in a poly[styrene‐block‐(ferrocenyl dimethylsilane)] (PS‐b‐PFDMS) diblock copolymer of lamellar micro‐morphology has been investigated. The PFDMS is shown to crystallize in a confined and grain‐by‐grain fashion. Here a ‘grain’ is defined as an ensemble of stacked lamellae wherein the PFDMS crystallization spreads quickly but stops at its surroundings. Such crystallization propagates not only along the PFDMS lamellae but across the amorphous PS layers as well. We suggest that conformational changes in the PS as induced by the PFDMS crystallization (‘squeezing transfer’) are responsible for the latter pathway of the crystallization's spread.
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