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Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks

[Image: see text] Due to their unique structural and mechanical properties, randomly cross-linked polymer networks play an important role in many different fields, ranging from cellular biology to industrial processes. In order to elucidate how these properties are controlled by the physical details...

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Autores principales: Sorichetti, Valerio, Ninarello, Andrea, Ruiz-Franco, José M., Hugouvieux, Virginie, Kob, Walter, Zaccarelli, Emanuela, Rovigatti, Lorenzo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8154883/
https://www.ncbi.nlm.nih.gov/pubmed/34054144
http://dx.doi.org/10.1021/acs.macromol.1c00176
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author Sorichetti, Valerio
Ninarello, Andrea
Ruiz-Franco, José M.
Hugouvieux, Virginie
Kob, Walter
Zaccarelli, Emanuela
Rovigatti, Lorenzo
author_facet Sorichetti, Valerio
Ninarello, Andrea
Ruiz-Franco, José M.
Hugouvieux, Virginie
Kob, Walter
Zaccarelli, Emanuela
Rovigatti, Lorenzo
author_sort Sorichetti, Valerio
collection PubMed
description [Image: see text] Due to their unique structural and mechanical properties, randomly cross-linked polymer networks play an important role in many different fields, ranging from cellular biology to industrial processes. In order to elucidate how these properties are controlled by the physical details of the network (e.g., chain-length and end-to-end distributions), we generate disordered phantom networks with different cross-linker concentrations C and initial densities ρ(init) and evaluate their elastic properties. We find that the shear modulus computed at the same strand concentration for networks with the same C, which determines the number of chains and the chain-length distribution, depends strongly on the preparation protocol of the network, here controlled by ρ(init). We rationalize this dependence by employing a generic stress–strain relation for polymer networks that does not rely on the specific form of the polymer end-to-end distance distribution. We find that the shear modulus of the networks is a nonmonotonic function of the density of elastically active strands, and that this behavior has a purely entropic origin. Our results show that if short chains are abundant, as it is always the case for randomly cross-linked polymer networks, the knowledge of the exact chain conformation distribution is essential for correctly predicting the elastic properties. Finally, we apply our theoretical approach to literature experimental data, qualitatively confirming our interpretations.
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spelling pubmed-81548832021-05-27 Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks Sorichetti, Valerio Ninarello, Andrea Ruiz-Franco, José M. Hugouvieux, Virginie Kob, Walter Zaccarelli, Emanuela Rovigatti, Lorenzo Macromolecules [Image: see text] Due to their unique structural and mechanical properties, randomly cross-linked polymer networks play an important role in many different fields, ranging from cellular biology to industrial processes. In order to elucidate how these properties are controlled by the physical details of the network (e.g., chain-length and end-to-end distributions), we generate disordered phantom networks with different cross-linker concentrations C and initial densities ρ(init) and evaluate their elastic properties. We find that the shear modulus computed at the same strand concentration for networks with the same C, which determines the number of chains and the chain-length distribution, depends strongly on the preparation protocol of the network, here controlled by ρ(init). We rationalize this dependence by employing a generic stress–strain relation for polymer networks that does not rely on the specific form of the polymer end-to-end distance distribution. We find that the shear modulus of the networks is a nonmonotonic function of the density of elastically active strands, and that this behavior has a purely entropic origin. Our results show that if short chains are abundant, as it is always the case for randomly cross-linked polymer networks, the knowledge of the exact chain conformation distribution is essential for correctly predicting the elastic properties. Finally, we apply our theoretical approach to literature experimental data, qualitatively confirming our interpretations. American Chemical Society 2021-04-14 2021-04-27 /pmc/articles/PMC8154883/ /pubmed/34054144 http://dx.doi.org/10.1021/acs.macromol.1c00176 Text en © 2021 The Authors. Published by American Chemical Society 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 Sorichetti, Valerio
Ninarello, Andrea
Ruiz-Franco, José M.
Hugouvieux, Virginie
Kob, Walter
Zaccarelli, Emanuela
Rovigatti, Lorenzo
Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks
title Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks
title_full Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks
title_fullStr Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks
title_full_unstemmed Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks
title_short Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks
title_sort effect of chain polydispersity on the elasticity of disordered polymer networks
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8154883/
https://www.ncbi.nlm.nih.gov/pubmed/34054144
http://dx.doi.org/10.1021/acs.macromol.1c00176
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