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Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range

A melt of short semi-flexible polymers with hard-sphere-type non-bonded interaction undergoes a first-order crystallisation transition at lower density than a melt of hard-sphere monomers or a flexible hard-sphere chain. In contrast to the flexible hard-sphere chains, the semi-flexible ones have an...

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Autor principal: Shakirov, Timur
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7515385/
http://dx.doi.org/10.3390/e21090856
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author Shakirov, Timur
author_facet Shakirov, Timur
author_sort Shakirov, Timur
collection PubMed
description A melt of short semi-flexible polymers with hard-sphere-type non-bonded interaction undergoes a first-order crystallisation transition at lower density than a melt of hard-sphere monomers or a flexible hard-sphere chain. In contrast to the flexible hard-sphere chains, the semi-flexible ones have an intrinsic stiffness energy scale, which determines the natural temperature scale of the system. In this paper, we investigate the effect of weak additional non-bonded interaction on the phase transition temperature. We study the system using the stochastic approximation Monte Carlo (SAMC) method to estimate the micro-canonical entropy of the system. Since the density of states in the purely hard-sphere non-bonded interaction case already covers 5600 orders of magnitude, we consider the effect of weak interactions as a perturbation. In this case, the system undergoes the same ordering transition with a temperature shift non-uniformly depending on the additional interaction. Short-range attractions impede ordering of the melt of semi-flexible polymers and decrease the transition temperature, whereas relatively long-range attractions assist ordering and shift the transition temperature to higher values, whereas weak repulsive interactions demonstrate an opposite effect on the transition temperature.
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spelling pubmed-75153852020-11-09 Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range Shakirov, Timur Entropy (Basel) Article A melt of short semi-flexible polymers with hard-sphere-type non-bonded interaction undergoes a first-order crystallisation transition at lower density than a melt of hard-sphere monomers or a flexible hard-sphere chain. In contrast to the flexible hard-sphere chains, the semi-flexible ones have an intrinsic stiffness energy scale, which determines the natural temperature scale of the system. In this paper, we investigate the effect of weak additional non-bonded interaction on the phase transition temperature. We study the system using the stochastic approximation Monte Carlo (SAMC) method to estimate the micro-canonical entropy of the system. Since the density of states in the purely hard-sphere non-bonded interaction case already covers 5600 orders of magnitude, we consider the effect of weak interactions as a perturbation. In this case, the system undergoes the same ordering transition with a temperature shift non-uniformly depending on the additional interaction. Short-range attractions impede ordering of the melt of semi-flexible polymers and decrease the transition temperature, whereas relatively long-range attractions assist ordering and shift the transition temperature to higher values, whereas weak repulsive interactions demonstrate an opposite effect on the transition temperature. MDPI 2019-09-01 /pmc/articles/PMC7515385/ http://dx.doi.org/10.3390/e21090856 Text en © 2019 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Shakirov, Timur
Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range
title Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range
title_full Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range
title_fullStr Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range
title_full_unstemmed Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range
title_short Crystallisation in Melts of Short, Semi-Flexible Hard-Sphere Polymer Chains: The Role of the Non-Bonded Interaction Range
title_sort crystallisation in melts of short, semi-flexible hard-sphere polymer chains: the role of the non-bonded interaction range
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7515385/
http://dx.doi.org/10.3390/e21090856
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