Nascent lateral habits of solution crystallization of poly(ethylene glycol)-block-polystyrene diblock copolymers

Some special habits of dilute solution-grown single crystals were introduced by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM) equipped with electron diffraction (ED). Well-defined block copolymers of poly(ethylene glycol)-block-polystyrene (PEG-b-PS) having predetermined molecular weight and narrow molecular weight distribution (1.06–1.08) were synthesized by atom transfer radical polymerization (ATRP). The single crystals of PEG-b-PS copolymers were grown in a mixed solvent comprised of chlorobenzene/octane and separately in amyl acetate, both using a self-seeding technique. We were capable to develop various growth fronts that resulted from different growth rates through infinitesimal temperature fluctuations. Elevated crystallization temperatures and a higher ratio of molecular weight of PS to that of PEG intensified the curvatures. The corresponding overall, crystalline, and amorphous thickness of a given single crystal, either in square and truncated shapes or with concave and convex lateral sides, had high consistency with each other.