Morphology, reorganization and stability of mesomorphic nanocrystals in isotactic polypropylene

The morphology and thermodynamic stability of crystals of isotactic polypropylene (iPP) were analyzed as a function of the path of crystallization by atomic force microscopy (AFM) and differential scanning calorimetry (DSC). Samples were melt-crystallized at different rates of cooling using a “controlled rapid cooling technique”, and subsequently annealed at elevated temperature. Mesomorphic equi-axed domains with a size less than 20 nm were obtained by fast cooling from the melt at a rate larger about 100 K s−1. These domains stabilize on heating by growing in chain direction and cross-chain direction, to reach a maximum size of about 40–50 nm at a temperature of 433 K, with the quasi-globular shape preserved. Annealing at 433 K additionally triggers formation of different types of lamellae. It is suggested that these lamellae either develop by coalescence of nodules, or by recrystallization from the melt. The transition from the disordered mesomorphic structure, evident at ambient temperature after fast crystallization, to monoclinic structure on heating at about 340 K occurs at local scale within existing crystals, and cannot be linked to complete melting of mesomorphic domains and recrystallization of the melt. The temperature of melting of initial mesomorphic domains, after reorganization at elevated temperature, is identical to the temperature of melting of rather perfect lamellae, obtained by initial slow melt-crystallization, followed by annealing. The close-to-identical temperatures of melting of these crystals of largely different shapes are confirmed by model calculations, using the Gibbs–Thomson equation. Modeling of the melting temperature reveals that nodular crystals, stabilized by annealing at high temperature, exhibit a similar fold-surface as lamellar crystals.