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Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets
Segmental dynamics in unentangled isotactic, syndiotactic, and atactic poly(methyl methacrylate) (i-, a-, and s-PMMA) melts confined between pristine graphene, reduced graphene oxide, RGO, or graphene oxide, GO, sheets is studied at various temperatures, well above glass transition temperature, via...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7962820/ https://www.ncbi.nlm.nih.gov/pubmed/33800419 http://dx.doi.org/10.3390/polym13050830 |
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author | Foroozani Behbahani, Alireza Harmandaris, Vagelis |
author_facet | Foroozani Behbahani, Alireza Harmandaris, Vagelis |
author_sort | Foroozani Behbahani, Alireza |
collection | PubMed |
description | Segmental dynamics in unentangled isotactic, syndiotactic, and atactic poly(methyl methacrylate) (i-, a-, and s-PMMA) melts confined between pristine graphene, reduced graphene oxide, RGO, or graphene oxide, GO, sheets is studied at various temperatures, well above glass transition temperature, via atomistic molecular dynamics simulations. The model RGO and GO sheets have different degrees of oxidization. The segmental dynamics is studied through the analysis of backbone torsional motions. In the vicinity of the model nanosheets (distances less than ≈2 nm), the dynamics slows down; the effect becomes significantly stronger with increasing the concentration of the surface functional groups, and hence increasing polymer/surface specific interactions. Upon decreasing temperature, the ratios of the interfacial segmental relaxation times to the respective bulk relaxation times increase, revealing the stronger temperature dependence of the interfacial segmental dynamics relative to the bulk dynamics. This heterogeneity in temperature dependence leads to the shortcoming of the time-temperature superposition principle for describing the segmental dynamics of the model confined melts. The alteration of the segmental dynamics at different distances, d, from the surfaces is described by a temperature shift, [Formula: see text] (roughly speaking, shift of a characteristic temperature). Next, to a given nanosheet, i-PMMA has a larger value of [Formula: see text] than a-PMMA and s-PMMA. This trend correlates with the better interfacial packing and longer trains of i-PMMA chains. The backbone torsional autocorrelation functions are shown in the frequency domain and are qualitatively compared to the experimental dielectric loss spectra for the segmental [Formula: see text] -relaxation in polymer nanocomposites. The [Formula: see text] (analogous of dielectric loss, [Formula: see text] , for torsional motion) curves of the model confined melts are broader (toward lower frequencies) and have lower amplitudes relative to the corresponding bulk curves; however, the peak frequencies of the [Formula: see text] curves are only slightly affected. |
format | Online Article Text |
id | pubmed-7962820 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-79628202021-03-17 Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets Foroozani Behbahani, Alireza Harmandaris, Vagelis Polymers (Basel) Article Segmental dynamics in unentangled isotactic, syndiotactic, and atactic poly(methyl methacrylate) (i-, a-, and s-PMMA) melts confined between pristine graphene, reduced graphene oxide, RGO, or graphene oxide, GO, sheets is studied at various temperatures, well above glass transition temperature, via atomistic molecular dynamics simulations. The model RGO and GO sheets have different degrees of oxidization. The segmental dynamics is studied through the analysis of backbone torsional motions. In the vicinity of the model nanosheets (distances less than ≈2 nm), the dynamics slows down; the effect becomes significantly stronger with increasing the concentration of the surface functional groups, and hence increasing polymer/surface specific interactions. Upon decreasing temperature, the ratios of the interfacial segmental relaxation times to the respective bulk relaxation times increase, revealing the stronger temperature dependence of the interfacial segmental dynamics relative to the bulk dynamics. This heterogeneity in temperature dependence leads to the shortcoming of the time-temperature superposition principle for describing the segmental dynamics of the model confined melts. The alteration of the segmental dynamics at different distances, d, from the surfaces is described by a temperature shift, [Formula: see text] (roughly speaking, shift of a characteristic temperature). Next, to a given nanosheet, i-PMMA has a larger value of [Formula: see text] than a-PMMA and s-PMMA. This trend correlates with the better interfacial packing and longer trains of i-PMMA chains. The backbone torsional autocorrelation functions are shown in the frequency domain and are qualitatively compared to the experimental dielectric loss spectra for the segmental [Formula: see text] -relaxation in polymer nanocomposites. The [Formula: see text] (analogous of dielectric loss, [Formula: see text] , for torsional motion) curves of the model confined melts are broader (toward lower frequencies) and have lower amplitudes relative to the corresponding bulk curves; however, the peak frequencies of the [Formula: see text] curves are only slightly affected. MDPI 2021-03-08 /pmc/articles/PMC7962820/ /pubmed/33800419 http://dx.doi.org/10.3390/polym13050830 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/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/ (https://creativecommons.org/licenses/by/4.0/) ). |
spellingShingle | Article Foroozani Behbahani, Alireza Harmandaris, Vagelis Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets |
title | Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets |
title_full | Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets |
title_fullStr | Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets |
title_full_unstemmed | Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets |
title_short | Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets |
title_sort | gradient of segmental dynamics in stereoregular poly(methyl methacrylate) melts confined between pristine or oxidized graphene sheets |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7962820/ https://www.ncbi.nlm.nih.gov/pubmed/33800419 http://dx.doi.org/10.3390/polym13050830 |
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