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 ρinit 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 ρinit. 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.

Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks / Sorichetti, V.; Ninarello, A.; Ruiz-Franco, J. M.; Hugouvieux, V.; Kob, W.; Zaccarelli, E.; Rovigatti, L.. - In: MACROMOLECULES. - ISSN 0024-9297. - 54:8(2021), pp. 3769-3779. [10.1021/acs.macromol.1c00176]

Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks

Sorichetti V.
;
Ruiz-Franco J. M.;Kob W.;Zaccarelli E.;Rovigatti L.
2021

Abstract

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 ρinit 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 ρinit. 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.
polymers; soft matter; elasticity
01 Pubblicazione su rivista::01a Articolo in rivista
Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks / Sorichetti, V.; Ninarello, A.; Ruiz-Franco, J. M.; Hugouvieux, V.; Kob, W.; Zaccarelli, E.; Rovigatti, L.. - In: MACROMOLECULES. - ISSN 0024-9297. - 54:8(2021), pp. 3769-3779. [10.1021/acs.macromol.1c00176]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1548201
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