Polymer crystallization at high melt-supercooling

Melt-processing of polymers typically involves rapid cooling and solidification of the melt at high supercooling. At such condition, crystallization may follow a homogeneous-nucleation path, and, as a consequence, semicrystalline morphologies and properties often are qualitatively different compared to crystallization at low melt-supercooling. This paper provides a comprehensive review of semicrystalline structures of both commodity and engineering polymers forming at different supercooling, and of our experimental approaches to gain such information. Specifically, fast scanning chip calorimetry is introduced as an invaluable tool to obtain information about the kinetics of nucleation and crystallization as well as, when coupled to microscopy or scattering techniques, about the morphology of semicrystalline polymers formed at any thermal condition. With the possibility of suppression of crystallization and vitrifying the entire melt, also glass-relaxation and -crystallization is discussed, important for understanding physical aging and long-term change of properties.