Abstract
Nucleation plays a vital role in polymer crystallization, in which chain connectivity and thus the multiple length and time scales make crystal nucleation of polymer chains an interesting but complex subject. Though the topic has been intensively studied in the past decades, there are still many open questions to answer. The final properties of semicrystalline polymer materials are affected by all of the following: the starting melt, paths of nucleation, organization of lamellar crystals and evolution of the final crystalline structures. In this viewpoint, we attempt to discuss some of the remaining open questions and corresponding concepts: non-equilibrated polymers, self-induced nucleation, microscopic kinetics of different processes, metastability of polymer lamellar crystals, hierarchical order and cooperativity involved in nucleation, etc. Addressing these open questions through a combination of novel concepts, new theories and advanced approaches provides a deeper understanding of the multifaceted process of crystal nucleation of polymers.
Highlights
Nucleation plays a vital role in polymer crystallization, in which chain connectivity and the multiple length and time scales make crystal nucleation of polymer chains an interesting but complex subject
We present and discuss a variety of mechanisms, which can initiate a polymer crystal: primary vs. secondary nucleation, self-nucleation vs. self-induced nucleation, self-seeding . . . We discuss how chain conformations and a change in topology in the amorphous melt may affect the mechanisms and the kinetics of nucleation of polymer crystals
The temperature coefficient of the selection of the thickness and the radial growth rate of polymer lamellar crystals are typically related to secondary nucleation, a process occurring repetitively on the growing crystal surface
Summary
The classical path for crystallization of any substance is via nucleation and growth. As shown by numerous experiments for many polymers, the connectivity of a large number of monomers in these chain-like molecules makes homogeneous nucleation to be an extremely slow process, often leading to highly unstable systems of low crystallinity prone to age and change in time. To eliminate this shortcoming of polymers, several approaches are available for enhancing the nucleation probability. We discuss how chain conformations and a change in topology in the amorphous melt may affect the mechanisms and the kinetics of nucleation of polymer crystals. A frank but respectful discussion of open questions in the field of polymer crystallization will help develop new ideas and foster new concepts
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