Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts

Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts

The time-temperature superposition (TTS) principle, employed extensively for the analysis of polymer dynamics, is based on the assumption that the different normal modes of polymer chains would experience identical temperature dependence. We aim to test the critical assumption for TTS principle by i...

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Autores principales: Hye Sol Kim, Taejin Kwon, Chung Bin Park, Bong June Sung
Formato: article
Lenguaje:EN
Publicado: MDPI AG 2021
Materias:
polymer melts
PEO
temperature dependence
Rouse model
conformation
Organic chemistry
QD241-441
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spelling oai:doaj.org-article:9c91e28ef3b14582a5d7ef744fad1b572021-11-25T18:49:44ZTemperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts10.3390/polym132240492073-4360https://doaj.org/article/9c91e28ef3b14582a5d7ef744fad1b572021-11-01T00:00:00Zhttps://www.mdpi.com/2073-4360/13/22/4049https://doaj.org/toc/2073-4360The time-temperature superposition (TTS) principle, employed extensively for the analysis of polymer dynamics, is based on the assumption that the different normal modes of polymer chains would experience identical temperature dependence. We aim to test the critical assumption for TTS principle by investigating poly(ethylene oxide) (PEO) melts, which have been considered excellent solid polyelectrolytes. In this work, we perform all-atom molecular dynamics simulations up to 300 ns at a range of temperatures for PEO melts. We find from our simulations that the conformations of strands of PEO chains in melts show ideal chain statistics when the strand consists of at least 10 monomers. At the temperature range of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>T</mi><mo>=</mo></mrow></semantics></math></inline-formula> 400 to 300 K, the mean-square displacements (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow></semantics></math></inline-formula>) of the centers of mass of chains enter the Fickian regime, i.e., <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow><mo>∼</mo><msup><mi>t</mi><mn>1</mn></msup></mrow></semantics></math></inline-formula>. On the other hand, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow></semantics></math></inline-formula> of the monomers of the chains scales as <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow><mo>∼</mo><msup><mi>t</mi><mrow><mn>1</mn><mo>/</mo><mn>2</mn></mrow></msup></mrow></semantics></math></inline-formula> at intermediate time scales as expected for the Rouse model. We investigate various relaxation modes of the polymer chains and their relaxation times (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>τ</mi><mi>n</mi></msub></semantics></math></inline-formula>), by calculating for each strand of <i>n</i> monomers. Interestingly, different normal modes of the PEO chains experience identical temperature dependence, thus indicating that the TTS principle would hold for the given temperature range.Hye Sol KimTaejin KwonChung Bin ParkBong June SungMDPI AGarticlepolymer meltsPEOtemperature dependenceRouse modelconformationOrganic chemistryQD241-441ENPolymers, Vol 13, Iss 4049, p 4049 (2021)
institution DOAJ
collection DOAJ
language EN
topic polymer melts
PEO
temperature dependence
Rouse model
conformation
Organic chemistry
QD241-441
spellingShingle polymer melts
PEO
temperature dependence
Rouse model
conformation
Organic chemistry
QD241-441
Hye Sol Kim
Taejin Kwon
Chung Bin Park
Bong June Sung
Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts
description The time-temperature superposition (TTS) principle, employed extensively for the analysis of polymer dynamics, is based on the assumption that the different normal modes of polymer chains would experience identical temperature dependence. We aim to test the critical assumption for TTS principle by investigating poly(ethylene oxide) (PEO) melts, which have been considered excellent solid polyelectrolytes. In this work, we perform all-atom molecular dynamics simulations up to 300 ns at a range of temperatures for PEO melts. We find from our simulations that the conformations of strands of PEO chains in melts show ideal chain statistics when the strand consists of at least 10 monomers. At the temperature range of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>T</mi><mo>=</mo></mrow></semantics></math></inline-formula> 400 to 300 K, the mean-square displacements (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow></semantics></math></inline-formula>) of the centers of mass of chains enter the Fickian regime, i.e., <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow><mo>∼</mo><msup><mi>t</mi><mn>1</mn></msup></mrow></semantics></math></inline-formula>. On the other hand, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow></semantics></math></inline-formula> of the monomers of the chains scales as <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mrow><mo>⟨</mo><mo>Δ</mo><msup><mi>r</mi><mn>2</mn></msup><mrow><mo>(</mo><mi>t</mi><mo>)</mo></mrow><mo>⟩</mo></mrow><mo>∼</mo><msup><mi>t</mi><mrow><mn>1</mn><mo>/</mo><mn>2</mn></mrow></msup></mrow></semantics></math></inline-formula> at intermediate time scales as expected for the Rouse model. We investigate various relaxation modes of the polymer chains and their relaxation times (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>τ</mi><mi>n</mi></msub></semantics></math></inline-formula>), by calculating for each strand of <i>n</i> monomers. Interestingly, different normal modes of the PEO chains experience identical temperature dependence, thus indicating that the TTS principle would hold for the given temperature range.
format article
author Hye Sol Kim
Taejin Kwon
Chung Bin Park
Bong June Sung
author_facet Hye Sol Kim
Taejin Kwon
Chung Bin Park
Bong June Sung
author_sort Hye Sol Kim
title Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts
title_short Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts
title_full Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts
title_fullStr Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts
title_full_unstemmed Temperature Dependence of Conformational Relaxation of Poly(ethylene oxide) Melts
title_sort temperature dependence of conformational relaxation of poly(ethylene oxide) melts
publisher MDPI AG
publishDate 2021
url https://doaj.org/article/9c91e28ef3b14582a5d7ef744fad1b57
work_keys_str_mv AT hyesolkim temperaturedependenceofconformationalrelaxationofpolyethyleneoxidemelts
AT taejinkwon temperaturedependenceofconformationalrelaxationofpolyethyleneoxidemelts
AT chungbinpark temperaturedependenceofconformationalrelaxationofpolyethyleneoxidemelts
AT bongjunesung temperaturedependenceofconformationalrelaxationofpolyethyleneoxidemelts
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