Morphological Control of Polymer Spherulites via Manipulating Radial Lamellar Organization upon Evaporative Crystallization: A Mini Review

Various spherulites or spherulitic crystals are widely encountered in polymeric materials when crystallized from viscous melts or concentrated solutions. However, the microstructures and growth processes are quite complicated and remain unclear and, thus, the formation mechanisms are rather elusive. Here, diverse kinds of spherulitic growths and patterns of typical polyesters via evaporative crystallization of solution-cast thin films are delineated after detailed investigating the microstructures and in situ following the developing processes. The spherulitic crystals produced under different evaporation conditions reflect variously optical features, such as the usual Maltese Cross, non-birefringent or half-birefringent concentric-rings, extinction spiral banding, and even a nested ring-banded pattern. Polymer spherulites are composed of stacks of radial fibrillar lamellae, and the diversity of bewitchingly spherulitic morphologies is dominated by the arrangement and organization of radial lamellae, which is predicted to be tunable by modulating the evaporative crystallization processes. The emergence of various types of spherulitic morphologies of the same polymer is attributed to a precise manipulation of the radial lamellar organization by a coupling of structural features and specific crystal evolving courses under confined evaporation environments. The present findings improve dramatically the understanding of the structural development and crystallization mechanism for emergence of diverse polymer spherulitic morphologies.