Int. J. Mol. Sci. 2013, 14(1), 332-358; doi:10.3390/ijms14010332

Spontaneous Crystallization in Athermal Polymer Packings

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Received: 28 November 2012; Accepted: 14 December 2012 / Published: 24 December 2012
(This article belongs to the Special Issue Molecular Self-Assembly 2012)
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.
Abstract: We review recent results from extensive simulations of the crystallization of athermal polymer packings. It is shown that above a certain packing density, and for sufficiently long simulations, all random assemblies of freely-jointed chains of tangent hard spheres of uniform size show a spontaneous transition into a crystalline phase. These polymer crystals adopt predominantly random hexagonal close packed morphologies. An analysis of the local environment around monomers based on the shape and size of the Voronoi polyhedra clearly shows that Voronoi cells become more spherical and more symmetric as the system transits to the ordered state. The change in the local environment leads to an increase in the monomer translational contribution to the entropy of the system, which acts as the driving force for the phase transition. A comparison of the crystallization of hard-sphere polymers and monomers highlights similarities and differences resulting from the constraints imposed by chain connectivity.
Keywords: polymer; crystallization; entropy; phase transition; Voronoi tesselation; simulation; Monte Carlo; hard sphere; random packing; crystal morphology
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MDPI and ACS Style

Karayiannis, N.C.; Foteinopoulou, K.; Laso, M. Spontaneous Crystallization in Athermal Polymer Packings. Int. J. Mol. Sci. 2013, 14, 332-358.

AMA Style

Karayiannis NC, Foteinopoulou K, Laso M. Spontaneous Crystallization in Athermal Polymer Packings. International Journal of Molecular Sciences. 2013; 14(1):332-358.

Chicago/Turabian Style

Karayiannis, Nikos C.; Foteinopoulou, Katerina; Laso, Manuel. 2013. "Spontaneous Crystallization in Athermal Polymer Packings." Int. J. Mol. Sci. 14, no. 1: 332-358.

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