Renkuan Cao, Fan Peng, Cui Nie, Yunhan Zhang, Hao Sun, Ziwei Liu, Tingyu Xu* and Liangbin Li*,
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引用次数: 0
Abstract
The debate surrounding preorders in the primary nucleation of polymer crystals has captivated scientists for decades. By constructing a cylindrical order parameter (COP), we observe a preordering-crystallization two-step nucleation process in a molecular dynamics simulation of polymer crystallization. Instead of the sharp interface between amorphous and crystalline regions assumed by classical nucleation theory (CNT), we observe a gradient COP profile that shifts toward higher COP values as the nucleus size increases. In nucleation dynamics, we depart from the Markov process described in the CNT, where single particles attach to and detach from nuclei without memory. Instead, we find that nucleation occurs through particle fluctuations with a memory effect, which is enhanced as the nucleus size increases, leading to positive feedback. This mechanism of nucleation via particle fluctuations with memory effect fundamentally diverges from CNT and previous nonclassical nucleation models, offering a new perspective on understanding the nucleation of polymers.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.