Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy

[EN] To study the nature and the cooperativity of the disulfide exchange mechanism in covalent adaptable networks, the dielectric and conductive properties of three membranes obtained by curing diglycidyl ether of bisphenol A (DGEBA) with hexamethylenediamine (HMDA), cystamine (CYS), or a mixture of...

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Autores: B. Pascual-Jose|||0000-0001-7562-916X, Teruel-Juanes, Roberto|||0000-0002-0190-4445, Ribes-Greus, A.|||0000-0003-2460-8291, De la Flor, S., Serra, A.
Formato: artículo
Fecha de publicación:2025
País:España
Recursos:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/220048
Acesso em linha:https://riunet.upv.es/handle/10251/220048
Access Level:acceso abierto
Palavra-chave:Disulfides
Covalent adaptable networks
Vitrimers
id ES_4fd1eb6ceabcdb9ae9b59e93edb7616b
oai_identifier_str oai:riunet.upv.es:10251/220048
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
title Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
spellingShingle Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
B. Pascual-Jose|||0000-0001-7562-916X
Disulfides
Covalent adaptable networks
Vitrimers
title_short Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
title_full Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
title_fullStr Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
title_full_unstemmed Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
title_sort Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopy
dc.creator.none.fl_str_mv B. Pascual-Jose|||0000-0001-7562-916X
Teruel-Juanes, Roberto|||0000-0002-0190-4445
Ribes-Greus, A.|||0000-0003-2460-8291
De la Flor, S.
Serra, A.
author B. Pascual-Jose|||0000-0001-7562-916X
author_facet B. Pascual-Jose|||0000-0001-7562-916X
Teruel-Juanes, Roberto|||0000-0002-0190-4445
Ribes-Greus, A.|||0000-0003-2460-8291
De la Flor, S.
Serra, A.
author_role author
author2 Teruel-Juanes, Roberto|||0000-0002-0190-4445
Ribes-Greus, A.|||0000-0003-2460-8291
De la Flor, S.
Serra, A.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Ingeniería Eléctrica
 Instituto Universitario de Investigación de Tecnología de los Materiales de la UPV
Escuela Politécnica Superior de Alcoy
Departamento de Ingeniería Electrónica
Departamento de Máquinas y Motores Térmicos
Escuela Técnica Superior de Ingeniería Aeroespacial y Diseño Industrial
Escuela Técnica Superior de Ingeniería Industrial
European Commission
Generalitat Valenciana
Generalitat de Catalunya
Agencia Estatal de Investigación
Universitat Politècnica de València
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Disulfides
Covalent adaptable networks
Vitrimers
topic Disulfides
Covalent adaptable networks
Vitrimers
description [EN] To study the nature and the cooperativity of the disulfide exchange mechanism in covalent adaptable networks, the dielectric and conductive properties of three membranes obtained by curing diglycidyl ether of bisphenol A (DGEBA) with hexamethylenediamine (HMDA), cystamine (CYS), or a mixture of both diamines in the same proportion were studied. Significant differences in the dielectric relaxation spectra of the three membranes were observed. In the low-temperature region, the dielectric spectra displayed two non-cooperative dielectric relaxations (gamma and beta). In the DGEBA/HMDA-CYS membrane, its relaxation function and activation energy are between those corresponding to the DGEBA/HDMA and DGEBA/CYS membranes, but their relationship does not depend linearly on the composition. In the high-temperature region, a dielectric relaxation of cooperative origin related to the glass transition (alpha) was observed in the membrane cured with hexamethylenediamine. However, the relaxation related to the glass transition overlaps with the exchange of the disulfide bonds in the membranes with cystamine. The analysis of the electric conductivity (6) reveals an abrupt increment that suggests a radicalmediated dissociative bond exchange reaction may be occurring. However, the analysis of the 6DC curves is indicative of an associative bond exchange reaction. The rapid formation of new associations among radicals is proposed to explain the vitrimer-like behaviour on these CYS-containing membranes.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-04-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/220048
url https://riunet.upv.es/handle/10251/220048
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Universitat Politècnica de València https://doi.org/10.13039/501100004233 PAID-10-23
Generalitat de Catalunya https://doi.org/10.13039/501100002809 2021-SGR-00154
Generalitat Valenciana https://doi.org/10.13039/501100003359 MFA%2F2022%2F041 Diseño y validación de materiales innovadores para su desarrollo como electrolitos de pilas de combustible de intercambio protónico en vehículos
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 PID2023-147128OB-C22
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 TED2021-131102B-C22
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento - No comercial - Sin obra derivada (by-nc-nd)
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento - No comercial - Sin obra derivada (by-nc-nd)
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Analysis of covalent adaptable networks Based on disulfide exchange through broadband dielectric spectroscopyB. Pascual-Jose|||0000-0001-7562-916XTeruel-Juanes, Roberto|||0000-0002-0190-4445Ribes-Greus, A.|||0000-0003-2460-8291De la Flor, S.Serra, A.DisulfidesCovalent adaptable networksVitrimers[EN] To study the nature and the cooperativity of the disulfide exchange mechanism in covalent adaptable networks, the dielectric and conductive properties of three membranes obtained by curing diglycidyl ether of bisphenol A (DGEBA) with hexamethylenediamine (HMDA), cystamine (CYS), or a mixture of both diamines in the same proportion were studied. Significant differences in the dielectric relaxation spectra of the three membranes were observed. In the low-temperature region, the dielectric spectra displayed two non-cooperative dielectric relaxations (gamma and beta). In the DGEBA/HMDA-CYS membrane, its relaxation function and activation energy are between those corresponding to the DGEBA/HDMA and DGEBA/CYS membranes, but their relationship does not depend linearly on the composition. In the high-temperature region, a dielectric relaxation of cooperative origin related to the glass transition (alpha) was observed in the membrane cured with hexamethylenediamine. However, the relaxation related to the glass transition overlaps with the exchange of the disulfide bonds in the membranes with cystamine. The analysis of the electric conductivity (6) reveals an abrupt increment that suggests a radicalmediated dissociative bond exchange reaction may be occurring. However, the analysis of the 6DC curves is indicative of an associative bond exchange reaction. The rapid formation of new associations among radicals is proposed to explain the vitrimer-like behaviour on these CYS-containing membranes.This study forms part of the Advanced Materials programme and was supported by the Spanish Ministry of Science and Innovation with funding from European Union NextGeneration EU (PRTR-C17.11) and by Generalitat Valenciana (MFA/2022/041) . The authors also thank Universitat Politecnica de Valencia for the grant PAID-10-23 SUB.1. The authors of the Universitat Rovira i Virgili would like to thank the funding of the projects TED2021-131102B-C22 and PID2023-147128OB-C22 provided by MCNI/AEI/https://doi.org/10.13039/501100011033 and European Union "NextGenerationEU"/PRTR. They also thank to the Generalitat de Catalunya (2021-SGR-00154) .ElsevierDepartamento de Ingeniería Eléctrica Instituto Universitario de Investigación de Tecnología de los Materiales de la UPVEscuela Politécnica Superior de AlcoyDepartamento de Ingeniería ElectrónicaDepartamento de Máquinas y Motores TérmicosEscuela Técnica Superior de Ingeniería Aeroespacial y Diseño IndustrialEscuela Técnica Superior de Ingeniería IndustrialEuropean CommissionGeneralitat ValencianaGeneralitat de CatalunyaAgencia Estatal de InvestigaciónUniversitat Politècnica de ValènciaRepositorio Institucional de la Universitat Politècnica de València Riunet20252025-04-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/220048reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengUniversitat Politècnica de València https://doi.org/10.13039/501100004233 PAID-10-23Generalitat de Catalunya https://doi.org/10.13039/501100002809 2021-SGR-00154Generalitat Valenciana https://doi.org/10.13039/501100003359 MFA%2F2022%2F041 Diseño y validación de materiales innovadores para su desarrollo como electrolitos de pilas de combustible de intercambio protónico en vehículosAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 PID2023-147128OB-C22Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 TED2021-131102B-C22open accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento - No comercial - Sin obra derivada (by-nc-nd) http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/2200482026-06-13T07:49:27Z
score 15,81155

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