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Vapor Swelling of Polymer Brushes Compared to Nongrafted Films

[Image: see text] Polymer brushes, coatings of polymers covalently end-grafted to a surface, have been proposed as a more stable alternative to traditional physisorbed coatings. However, when such coatings are applied in settings such as vapor sensing and gas separation technologies, their responsiv...

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Autores principales: Ritsema van Eck, Guido C., Kiens, Ellen M., Veldscholte, Lars B., Brió Pérez, Maria, de Beer, Sissi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9671043/
https://www.ncbi.nlm.nih.gov/pubmed/36331903
http://dx.doi.org/10.1021/acs.langmuir.2c01889
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author Ritsema van Eck, Guido C.
Kiens, Ellen M.
Veldscholte, Lars B.
Brió Pérez, Maria
de Beer, Sissi
author_facet Ritsema van Eck, Guido C.
Kiens, Ellen M.
Veldscholte, Lars B.
Brió Pérez, Maria
de Beer, Sissi
author_sort Ritsema van Eck, Guido C.
collection PubMed
description [Image: see text] Polymer brushes, coatings of polymers covalently end-grafted to a surface, have been proposed as a more stable alternative to traditional physisorbed coatings. However, when such coatings are applied in settings such as vapor sensing and gas separation technologies, their responsiveness to solvent vapors becomes an important consideration. It can be anticipated that the end-anchoring in polymer brushes reduces the translational entropy of the polymers and instead introduces an entropic penalty against stretching when vapor is absorbed. Therefore, swelling can be expected to be diminished in brushes compared to nongrafted films. Here, we study the effect of the anchoring-constraint on vapor sorption in polymer coatings using coarse-grained molecular dynamics simulations as well as humidity-controlled ellipsometry on chemically identical polymer brushes and nongrafted films. We find a qualitative agreement between simulations and experiments, with both indicating that brushes certainly swell less than physisorbed films, although this effect is minor for common grafting densities. Our results imply that polymer brushes indeed hold great potential for the intended applications.
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spelling pubmed-96710432022-11-18 Vapor Swelling of Polymer Brushes Compared to Nongrafted Films Ritsema van Eck, Guido C. Kiens, Ellen M. Veldscholte, Lars B. Brió Pérez, Maria de Beer, Sissi Langmuir [Image: see text] Polymer brushes, coatings of polymers covalently end-grafted to a surface, have been proposed as a more stable alternative to traditional physisorbed coatings. However, when such coatings are applied in settings such as vapor sensing and gas separation technologies, their responsiveness to solvent vapors becomes an important consideration. It can be anticipated that the end-anchoring in polymer brushes reduces the translational entropy of the polymers and instead introduces an entropic penalty against stretching when vapor is absorbed. Therefore, swelling can be expected to be diminished in brushes compared to nongrafted films. Here, we study the effect of the anchoring-constraint on vapor sorption in polymer coatings using coarse-grained molecular dynamics simulations as well as humidity-controlled ellipsometry on chemically identical polymer brushes and nongrafted films. We find a qualitative agreement between simulations and experiments, with both indicating that brushes certainly swell less than physisorbed films, although this effect is minor for common grafting densities. Our results imply that polymer brushes indeed hold great potential for the intended applications. American Chemical Society 2022-11-04 2022-11-15 /pmc/articles/PMC9671043/ /pubmed/36331903 http://dx.doi.org/10.1021/acs.langmuir.2c01889 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Ritsema van Eck, Guido C.
Kiens, Ellen M.
Veldscholte, Lars B.
Brió Pérez, Maria
de Beer, Sissi
Vapor Swelling of Polymer Brushes Compared to Nongrafted Films
title Vapor Swelling of Polymer Brushes Compared to Nongrafted Films
title_full Vapor Swelling of Polymer Brushes Compared to Nongrafted Films
title_fullStr Vapor Swelling of Polymer Brushes Compared to Nongrafted Films
title_full_unstemmed Vapor Swelling of Polymer Brushes Compared to Nongrafted Films
title_short Vapor Swelling of Polymer Brushes Compared to Nongrafted Films
title_sort vapor swelling of polymer brushes compared to nongrafted films
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9671043/
https://www.ncbi.nlm.nih.gov/pubmed/36331903
http://dx.doi.org/10.1021/acs.langmuir.2c01889
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