(PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation

In this work, we study how chain topology can induce different polymorphic behaviors in poly(vinylidene fluoride) (PVDF)-based materials. A linear PVDF precursor with two azido groups at the junction point, (PVDFx-N3)2 and three 4-miktoarm star copolymers (PVDFx)2-b-(PEOy)2 with two poly(ethylene ox...

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Detalles Bibliográficos
Autores: María, Nicolás, Patil, Yogesh, Polymeropoulos, George, Peshkov, Anatoly, Rodionov, Valentin, Maiz, Jon, Hadjichristidis, Nikos, Müller, Alejandro J.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/303397
Acceso en línea:http://hdl.handle.net/10261/303397
Access Level:acceso abierto
Palabra clave:PVDF
Miktoarm star
Block copolymers
Isothermal crystallization
β-phase
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dc.title.none.fl_str_mv (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
title (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
spellingShingle (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
María, Nicolás
PVDF
Miktoarm star
Block copolymers
Isothermal crystallization
β-phase
title_short (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
title_full (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
title_fullStr (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
title_full_unstemmed (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
title_sort (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formation
dc.creator.none.fl_str_mv María, Nicolás
Patil, Yogesh
Polymeropoulos, George
Peshkov, Anatoly
Rodionov, Valentin
Maiz, Jon
Hadjichristidis, Nikos
Müller, Alejandro J.
author María, Nicolás
author_facet María, Nicolás
Patil, Yogesh
Polymeropoulos, George
Peshkov, Anatoly
Rodionov, Valentin
Maiz, Jon
Hadjichristidis, Nikos
Müller, Alejandro J.
author_role author
author2 Patil, Yogesh
Polymeropoulos, George
Peshkov, Anatoly
Rodionov, Valentin
Maiz, Jon
Hadjichristidis, Nikos
Müller, Alejandro J.
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Eusko Jaurlaritza
Donostia International Physics Center
Fundación Iberdrola
King Abdullah University of Science and Technology
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv PVDF
Miktoarm star
Block copolymers
Isothermal crystallization
β-phase
topic PVDF
Miktoarm star
Block copolymers
Isothermal crystallization
β-phase
description In this work, we study how chain topology can induce different polymorphic behaviors in poly(vinylidene fluoride) (PVDF)-based materials. A linear PVDF precursor with two azido groups at the junction point, (PVDFx-N3)2 and three 4-miktoarm star copolymers (PVDFx)2-b-(PEOy)2 with two poly(ethylene oxide) (PEO) and two PVDF arms were synthesized and employed in this study. The amphiphilic miktoarm copolymers were prepared by a combination of anionic ring-opening polymerization, iodine transfer radical polymerization (ITP), and copper-catalyzed azide-alkyne cycloaddition (CuAAC). They have practically similar overall molar mass but different compositions, ideal for performing bulk morphology and crystallization investigations. The isothermal overall crystallization kinetics of the PVDF and PEO arms of the 4-miktoarm star copolymers and representative PEO and PVDF precursors was determined by Differential Scanning Calorimetry (DSC). The results indicate that the star arms crystallized faster than the equivalent precursors as the kinetics are dominated by nucleation effects. The phases formed by the PVDF components in the materials examined were analyzed by studying their melting behavior by DSC, their superstructural morphology by Polarized Light Optical Microscopy (PLOM), and the phase structure by Fourier Transform Infrared Spectroscopy (FTIR). The linear PVDF and (PVDF29-N3)2, exhibited α, β and γ-phases (with a majority of β-phase formation) during melting after isothermal crystallization. The ratio of the different phases depends on the crystallization temperature. An analysis of the multiple melting behavior indicated that the sample forms both α and β-phases initially, and the α-phase partially transforms into the γ-phase during isothermal crystallization when the temperature of crystallization increases. We found a remarkable behavior for the 4-miktoarm star copolymers, as the PVDF arms only form the ferroelectric β-phase when all three materials were isothermally crystallized regardless of the crystallization temperature employed. The presence of the polymorphism in the PVDF was detected by DSC, PLOM, and FTIR. Hence, we have shown that tailoring chain topology in PVDF copolymers can lead to exclusive β-phase formation, a path that can be exploited for future piezoelectric applications.
publishDate 2022
dc.date.none.fl_str_mv 2022
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/303397
url http://hdl.handle.net/10261/303397
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113045GB-C21
European Polymer Journal
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1016/j.eurpolymj.2022.111506
https://doi.org/10.1016/j.eurpolymj.2022.111506

dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling (PVDF)2(PEO)2 miktoarm star copolymers: Synthesis and isothermal crystallization leading to exclusive β-phase formationMaría, NicolásPatil, YogeshPolymeropoulos, GeorgePeshkov, AnatolyRodionov, ValentinMaiz, JonHadjichristidis, NikosMüller, Alejandro J.PVDFMiktoarm starBlock copolymersIsothermal crystallizationβ-phaseIn this work, we study how chain topology can induce different polymorphic behaviors in poly(vinylidene fluoride) (PVDF)-based materials. A linear PVDF precursor with two azido groups at the junction point, (PVDFx-N3)2 and three 4-miktoarm star copolymers (PVDFx)2-b-(PEOy)2 with two poly(ethylene oxide) (PEO) and two PVDF arms were synthesized and employed in this study. The amphiphilic miktoarm copolymers were prepared by a combination of anionic ring-opening polymerization, iodine transfer radical polymerization (ITP), and copper-catalyzed azide-alkyne cycloaddition (CuAAC). They have practically similar overall molar mass but different compositions, ideal for performing bulk morphology and crystallization investigations. The isothermal overall crystallization kinetics of the PVDF and PEO arms of the 4-miktoarm star copolymers and representative PEO and PVDF precursors was determined by Differential Scanning Calorimetry (DSC). The results indicate that the star arms crystallized faster than the equivalent precursors as the kinetics are dominated by nucleation effects. The phases formed by the PVDF components in the materials examined were analyzed by studying their melting behavior by DSC, their superstructural morphology by Polarized Light Optical Microscopy (PLOM), and the phase structure by Fourier Transform Infrared Spectroscopy (FTIR). The linear PVDF and (PVDF29-N3)2, exhibited α, β and γ-phases (with a majority of β-phase formation) during melting after isothermal crystallization. The ratio of the different phases depends on the crystallization temperature. An analysis of the multiple melting behavior indicated that the sample forms both α and β-phases initially, and the α-phase partially transforms into the γ-phase during isothermal crystallization when the temperature of crystallization increases. We found a remarkable behavior for the 4-miktoarm star copolymers, as the PVDF arms only form the ferroelectric β-phase when all three materials were isothermally crystallized regardless of the crystallization temperature employed. The presence of the polymorphism in the PVDF was detected by DSC, PLOM, and FTIR. Hence, we have shown that tailoring chain topology in PVDF copolymers can lead to exclusive β-phase formation, a path that can be exploited for future piezoelectric applications.We acknowledge funding from MICINN through grant PID2020-113045GB-C21. We would also like to acknowledge the support of the Basque Government through grant IT1503-22. N. M. thankfully acknowledges his Ph.D. fellowship from the POLYMAT Basque Center for Macromolecular Design and Engineering. J. M. acknowledges partial financial support from the IBERDROLA Foundation. Y.P., G.P., A.P., V.R., and N.H. thankfully acknowledge the support of King Abdullah University of Science and Technology (KAUST).Peer reviewedElsevierMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Eusko JaurlaritzaDonostia International Physics CenterFundación IberdrolaKing Abdullah University of Science and TechnologyConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/303397reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113045GB-C21European Polymer JournalThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1016/j.eurpolymj.2022.111506https://doi.org/10.1016/j.eurpolymj.2022.111506Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3033972026-05-22T06:33:51Z
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