Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers
Achieving a unique combination of stiffness, strength, extensibility, and toughness in sol-cast poly(urethane–urea) (PU) copolymer films is a challenge since these properties are—in general—mutually exclusive. Here we demonstrate that geometric confinement of the basic building blocks controls stiff...
| Autores: | , , , , , , , |
|---|---|
| Formato: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Recursos: | Universitat Politècnica de Catalunya (UPC) |
| Repositorio: | UPCommons. Portal del coneixement obert de la UPC |
| Idioma: | inglés |
| OAI Identifier: | oai:upcommons.upc.edu:2117/377852 |
| Acesso em linha: | https://hdl.handle.net/2117/377852 https://dx.doi.org/10.1021/acs.macromol.1c00596 |
| Access Level: | acceso abierto |
| Palavra-chave: | Copolymers Crystallization Crystals Organic polymers Urea Copolímers Cristal·lització Àrees temàtiques de la UPC::Enginyeria dels materials |
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Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymersOguz, OguzhanCandau, Nicolas|||0000-0002-1559-8696Stoclet, GrégorySimsek, EremKosak Soz, CaglaYilgor, EmelYilgor, IskenderMenceloglu, Yusuf Z.CopolymersCrystallizationCopolymersCrystallizationCrystalsOrganic polymersUreaCopolímersCristal·litzacióÀrees temàtiques de la UPC::Enginyeria dels materialsAchieving a unique combination of stiffness, strength, extensibility, and toughness in sol-cast poly(urethane–urea) (PU) copolymer films is a challenge since these properties are—in general—mutually exclusive. Here we demonstrate that geometric confinement of the basic building blocks controls stiffness, strength, extensibility, and toughness in PU films. Our results suggest that the severity of geometric confinement can be tuned by adjusting (i) soft segment molecular weight (SSMW) and (ii) drying temperature (DT) thanks to their effects on the structure formation via microphase separation and/or (confined and/or bulk) crystallization. It is therefore possible to produce (i) soft (no notable confinement) and (ii) stiff, strong, extensible, and tough (severe confinement) materials without changing any other parameter except SSMW and DT. The former has a typical physically cross-linked network and shows a well-defined elastomeric behavior with an elastic modulus (E) of 5–20 MPa, a tensile strength (smax) of 30–35 MPa, an extensibility (e) of 1000–1300%, and a toughness (W) of 90–180 MJ m–3. The latter, on the other hand, possesses an elegant hierarchical structure containing tightly packed secondary structures (72-helix, 41-helix, and antiparallel ß-sheets) and displays an elastoplastic behavior with an E of 400–700 MPa, a smax of 45–55 MPa, an e of 650–850%, and a W of 200–250 MJ m–3. Hence, our findings may be of interest in designing advanced materials containing synthetic replica of the secondary structures found in protein-based materials. The structure formation in the materials with this structural hierarchy is driven by the confined crystallization of helical poly(ethylene oxide) (PEO) chains in subnanometer urea channels, which—to the best of our knowledge—is a phenomenon well-known in host–guest systems but has not yet demonstrated in PU copolymers, and complemented by the “bulk” crystallization of PEO and/or the microphase separation.Peer ReviewedAmerican Chemical Society (ACS)20212021-05-2520222022-12-12journal articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/2117/377852https://dx.doi.org/10.1021/acs.macromol.1c00596reponame:UPCommons. Portal del coneixement obert de la UPCinstname:Universitat Politècnica de Catalunya (UPC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:upcommons.upc.edu:2117/3778522026-05-27T15:37:01Z |
| dc.title.none.fl_str_mv |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| title |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| spellingShingle |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers Oguz, Oguzhan Copolymers Crystallization Copolymers Crystallization Crystals Organic polymers Urea Copolímers Cristal·lització Àrees temàtiques de la UPC::Enginyeria dels materials |
| title_short |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| title_full |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| title_fullStr |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| title_full_unstemmed |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| title_sort |
Geometric confinement controls stiffness, strength, extensibility, and toughness in poly(urethane–urea) copolymers |
| dc.creator.none.fl_str_mv |
Oguz, Oguzhan Candau, Nicolas|||0000-0002-1559-8696 Stoclet, Grégory Simsek, Erem Kosak Soz, Cagla Yilgor, Emel Yilgor, Iskender Menceloglu, Yusuf Z. |
| author |
Oguz, Oguzhan |
| author_facet |
Oguz, Oguzhan Candau, Nicolas|||0000-0002-1559-8696 Stoclet, Grégory Simsek, Erem Kosak Soz, Cagla Yilgor, Emel Yilgor, Iskender Menceloglu, Yusuf Z. |
| author_role |
author |
| author2 |
Candau, Nicolas|||0000-0002-1559-8696 Stoclet, Grégory Simsek, Erem Kosak Soz, Cagla Yilgor, Emel Yilgor, Iskender Menceloglu, Yusuf Z. |
| author2_role |
author author author author author author author |
| dc.subject.none.fl_str_mv |
Copolymers Crystallization Copolymers Crystallization Crystals Organic polymers Urea Copolímers Cristal·lització Àrees temàtiques de la UPC::Enginyeria dels materials |
| topic |
Copolymers Crystallization Copolymers Crystallization Crystals Organic polymers Urea Copolímers Cristal·lització Àrees temàtiques de la UPC::Enginyeria dels materials |
| description |
Achieving a unique combination of stiffness, strength, extensibility, and toughness in sol-cast poly(urethane–urea) (PU) copolymer films is a challenge since these properties are—in general—mutually exclusive. Here we demonstrate that geometric confinement of the basic building blocks controls stiffness, strength, extensibility, and toughness in PU films. Our results suggest that the severity of geometric confinement can be tuned by adjusting (i) soft segment molecular weight (SSMW) and (ii) drying temperature (DT) thanks to their effects on the structure formation via microphase separation and/or (confined and/or bulk) crystallization. It is therefore possible to produce (i) soft (no notable confinement) and (ii) stiff, strong, extensible, and tough (severe confinement) materials without changing any other parameter except SSMW and DT. The former has a typical physically cross-linked network and shows a well-defined elastomeric behavior with an elastic modulus (E) of 5–20 MPa, a tensile strength (smax) of 30–35 MPa, an extensibility (e) of 1000–1300%, and a toughness (W) of 90–180 MJ m–3. The latter, on the other hand, possesses an elegant hierarchical structure containing tightly packed secondary structures (72-helix, 41-helix, and antiparallel ß-sheets) and displays an elastoplastic behavior with an E of 400–700 MPa, a smax of 45–55 MPa, an e of 650–850%, and a W of 200–250 MJ m–3. Hence, our findings may be of interest in designing advanced materials containing synthetic replica of the secondary structures found in protein-based materials. The structure formation in the materials with this structural hierarchy is driven by the confined crystallization of helical poly(ethylene oxide) (PEO) chains in subnanometer urea channels, which—to the best of our knowledge—is a phenomenon well-known in host–guest systems but has not yet demonstrated in PU copolymers, and complemented by the “bulk” crystallization of PEO and/or the microphase separation. |
| publishDate |
2021 |
| dc.date.none.fl_str_mv |
2021 2021-05-25 2022 2022-12-12 |
| dc.type.none.fl_str_mv |
journal article http://purl.org/coar/resource_type/c_6501 AM http://purl.org/coar/version/c_ab4af688f83e57aa |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
https://hdl.handle.net/2117/377852 https://dx.doi.org/10.1021/acs.macromol.1c00596 |
| url |
https://hdl.handle.net/2117/377852 https://dx.doi.org/10.1021/acs.macromol.1c00596 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
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info:eu-repo/semantics/openAccess |
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open access http://purl.org/coar/access_right/c_abf2 Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
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openAccess |
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application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society (ACS) |
| publisher.none.fl_str_mv |
American Chemical Society (ACS) |
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reponame:UPCommons. Portal del coneixement obert de la UPC instname:Universitat Politècnica de Catalunya (UPC) |
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Universitat Politècnica de Catalunya (UPC) |
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UPCommons. Portal del coneixement obert de la UPC |
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UPCommons. Portal del coneixement obert de la UPC |
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15,301603 |