Herranz, M.; Foteinopoulou, K.; Karayiannis, N.C.; Laso, M. Polymorphism and Perfection in Crystallization of Hard Sphere Polymers. Polymers2022, 14, 4435.
Herranz, M.; Foteinopoulou, K.; Karayiannis, N.C.; Laso, M. Polymorphism and Perfection in Crystallization of Hard Sphere Polymers. Polymers 2022, 14, 4435.
Herranz, M.; Foteinopoulou, K.; Karayiannis, N.C.; Laso, M. Polymorphism and Perfection in Crystallization of Hard Sphere Polymers. Polymers2022, 14, 4435.
Herranz, M.; Foteinopoulou, K.; Karayiannis, N.C.; Laso, M. Polymorphism and Perfection in Crystallization of Hard Sphere Polymers. Polymers 2022, 14, 4435.
Abstract
We present results on the spontaneous crystallization of freely-jointed polymers of hard spheres obtained in an unprecedentedly long Monte Carlo (MC) simulation on a system of 54 chains of 1000 monomers. Starting from a purely amorphous configuration and after a transitory dominance of the hexagonal closed packed (HCP) polymorph, the system crystallizes in a final, stable, face centered cubic (FCC) crystal of very high perfection. Through refined metrics we gauge the degree of ordering and identify the regions of the phase transition and the corresponding morphologies. An analysis of chain conformational characteristics, of the spatial distribution of monomers and of the volume accessible to them shows that the phase transition is caused by an increase in translational entropy that is larger than the loss of conformational entropy of the chains in the crystal compared to the amorphous state. Polymer chains in the crystal adopt ideal random walk statistics as their great length renders local conformational details, imposed by the geometry of the FCC crystal, irrelevant.
Keywords
n/a; Hard Sphere; Crystallization; Entropy-driven phenomena; packing, polymer, molecular simulation, phase transition, face centered-cubic, hexagonal close packed; random walk; colloids; crystal perfection
Subject
Physical Sciences, Atomic and Molecular Physics
Copyright:
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
