H.N. Chávez Thielemann , J.A.W. van Dommelen , L.E. Govaert , M. Hütter
{"title":"Molecular dynamics analysis of iPP-polymorphs; Investigating thermal expansion and elastic properties","authors":"H.N. Chávez Thielemann , J.A.W. van Dommelen , L.E. Govaert , M. Hütter","doi":"10.1016/j.polymer.2024.127853","DOIUrl":null,"url":null,"abstract":"<div><div>The elastic properties of <span><math><mi>α</mi></math></span> and <span><math><mi>β</mi></math></span> crystals of isotactic polypropylene are obtained by molecular dynamics simulations of a crystalline domain resembling an infinite crystal. The helical polymer chains are modeled with an all-atom force-field. The assessment of the pristine <span><math><msub><mrow><mi>α</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> lattice agreed with published results of structure, density, thermal expansion, and stiffness. Monoclinic <span><math><mi>α</mi></math></span> systems with particular imperfections are sampled to assess the effect of defects on conformational stability and elastic properties. The sensitivity of elastic moduli with temperature correlates with the helicity disruption: the more chain-conformational defects, the stronger the decrease in elastic modulus. The non-perfect chiral up-down <span><math><msub><mrow><mi>α</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span> lattice and the arrangement with one vacancy also display a lower stiffness than <span><math><msub><mrow><mi>α</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>, which can be attributed to a less dense crystal and decreased inter-chain cooperative forces due to periodicity disruption.</div><div>Two variations of the metastable <span><math><mi>β</mi></math></span> modification were sampled to assess the most energetically favorable configurations. Then, both were subjected to the same procedure, validated first for <span><math><mi>α</mi></math></span>. A trigonal mono-chiral system, <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>, and a stable bi-chiral one with a four-chain frustrated orthorhombic cell, <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span>, were found, both presenting novel characteristics. Both <span><math><mi>β</mi></math></span> structures display a less stable conformation than <span><math><msub><mrow><mi>α</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>, observed by a higher specific volume, a lower transition temperature, and a more significant dependence of the elastic moduli with temperature. Remarkably, the mono-chiral <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> crystal showed higher elastic modulus than any other crystal below room temperature, related to a more efficient global methyl interlocking between chains. The fact that the experimental value for the density of the <span><math><mi>β</mi></math></span>-kind of crystal is in between the values that we obtained from the simulations of <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> and <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span> implies that the experimental observations consist of both of these <span><math><mi>β</mi></math></span> crystals, where <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>1</mn></mrow></msub></math></span> might work as an interface between monochiral <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> layers.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"316 ","pages":"Article 127853"},"PeriodicalIF":4.1000,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0032386124011893","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
The elastic properties of and crystals of isotactic polypropylene are obtained by molecular dynamics simulations of a crystalline domain resembling an infinite crystal. The helical polymer chains are modeled with an all-atom force-field. The assessment of the pristine lattice agreed with published results of structure, density, thermal expansion, and stiffness. Monoclinic systems with particular imperfections are sampled to assess the effect of defects on conformational stability and elastic properties. The sensitivity of elastic moduli with temperature correlates with the helicity disruption: the more chain-conformational defects, the stronger the decrease in elastic modulus. The non-perfect chiral up-down lattice and the arrangement with one vacancy also display a lower stiffness than , which can be attributed to a less dense crystal and decreased inter-chain cooperative forces due to periodicity disruption.
Two variations of the metastable modification were sampled to assess the most energetically favorable configurations. Then, both were subjected to the same procedure, validated first for . A trigonal mono-chiral system, , and a stable bi-chiral one with a four-chain frustrated orthorhombic cell, , were found, both presenting novel characteristics. Both structures display a less stable conformation than , observed by a higher specific volume, a lower transition temperature, and a more significant dependence of the elastic moduli with temperature. Remarkably, the mono-chiral crystal showed higher elastic modulus than any other crystal below room temperature, related to a more efficient global methyl interlocking between chains. The fact that the experimental value for the density of the -kind of crystal is in between the values that we obtained from the simulations of and implies that the experimental observations consist of both of these crystals, where might work as an interface between monochiral layers.
期刊介绍:
Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics.
The main scope is covered but not limited to the following core areas:
Polymer Materials
Nanocomposites and hybrid nanomaterials
Polymer blends, films, fibres, networks and porous materials
Physical Characterization
Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films
Polymer Engineering
Advanced multiscale processing methods
Polymer Synthesis, Modification and Self-assembly
Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization
Technological Applications
Polymers for energy generation and storage
Polymer membranes for separation technology
Polymers for opto- and microelectronics.