Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest

We have combined X-ray diffraction, neutron diffraction with polarization analysis, small-angle neutron scattering (SANS), neutron elastic fixed window scans (EFWS), and differential scanning calorimetry (DSC) to investigate polymeric blends of industrial interest composed by isotopically labeled st...

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Autores: Shafqat, Numera, Alegría Loinaz, Angel María, Malicki, Nicolas, Dronet, Severin, Natali, Francesca, Mangin-Thro, Lucile, Porcar, Lionel, Arbe Méndez, María Aranzazu, Colmenero de León, Juan
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/60946
Acceso en línea:http://hdl.handle.net/10810/60946
Access Level:acceso abierto
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spelling Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial InterestShafqat, NumeraAlegría Loinaz, Angel MaríaMalicki, NicolasDronet, SeverinNatali, FrancescaMangin-Thro, LucilePorcar, LionelArbe Méndez, María AranzazuColmenero de León, JuanWe have combined X-ray diffraction, neutron diffraction with polarization analysis, small-angle neutron scattering (SANS), neutron elastic fixed window scans (EFWS), and differential scanning calorimetry (DSC) to investigate polymeric blends of industrial interest composed by isotopically labeled styrene–butadiene rubber (SBR) and polystyrene (PS) oligomers of size smaller than the Kuhn length. The EFWS are sensitive to the onset of liquid-like motions across the calorimetric glass transition, allowing the selective determination of the “microscopic” effective glass transitions of the components. These are compared with the “macroscopic” counterparts disentangled by the analysis of the DSC results in terms of a model based on the effects of thermally driven concentration fluctuations and self-concentration. At the microscopic level, the mixtures are dynamically heterogeneous for blends with intermediate concentrations or rich in PS, while the sample with highest content of the fast SBR component looks as dynamically homogeneous. Moreover, the combination of SANS and DSC has allowed determining the relevant length scale for the α-relaxation through its loss of equilibrium to be ≈30 Å. This is compared with the different characteristic length scales that can be identified in these complex mixtures from structural, thermodynamical, and dynamical points of view because of the combined approach followed. We also discuss the sources of the non-Gaussian effects observed for the atomic displacements and the applicability of a Lindemann-like criterion in these materials.We thank Marc Couty for fruitful discussions and Karine Vernay (Michelin Advanced Research) for dSBR synthesis. The authors acknowledge Grant PID2021-123438NB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”, as well as financial support of Eusko Jaurlaritza (code: IT1566-22) and from the IKUR Strategy under the collaboration agreement between Ikerbasque Foundation and the Materials Physics Center on behalf of the Department of Education of the Basque Government. We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).American Chemical Society202320232023info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/60946reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MICINN/PID2021-123438NB-I00/https://pubs.acs.org/doi/10.1021/acs.macromol.2c02368info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/3.0/es/© 2023 The Authors. Published by American Chemical Society. Attribution 4.0 International (CC BY 4.0)Atribución 3.0 Españaoai:addi.ehu.eus:10810/609462026-06-18T09:23:17Z
dc.title.none.fl_str_mv Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
title Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
spellingShingle Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
Shafqat, Numera
title_short Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
title_full Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
title_fullStr Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
title_full_unstemmed Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
title_sort Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest
dc.creator.none.fl_str_mv Shafqat, Numera
Alegría Loinaz, Angel María
Malicki, Nicolas
Dronet, Severin
Natali, Francesca
Mangin-Thro, Lucile
Porcar, Lionel
Arbe Méndez, María Aranzazu
Colmenero de León, Juan
author Shafqat, Numera
author_facet Shafqat, Numera
Alegría Loinaz, Angel María
Malicki, Nicolas
Dronet, Severin
Natali, Francesca
Mangin-Thro, Lucile
Porcar, Lionel
Arbe Méndez, María Aranzazu
Colmenero de León, Juan
author_role author
author2 Alegría Loinaz, Angel María
Malicki, Nicolas
Dronet, Severin
Natali, Francesca
Mangin-Thro, Lucile
Porcar, Lionel
Arbe Méndez, María Aranzazu
Colmenero de León, Juan
author2_role author
author
author
author
author
author
author
author
description We have combined X-ray diffraction, neutron diffraction with polarization analysis, small-angle neutron scattering (SANS), neutron elastic fixed window scans (EFWS), and differential scanning calorimetry (DSC) to investigate polymeric blends of industrial interest composed by isotopically labeled styrene–butadiene rubber (SBR) and polystyrene (PS) oligomers of size smaller than the Kuhn length. The EFWS are sensitive to the onset of liquid-like motions across the calorimetric glass transition, allowing the selective determination of the “microscopic” effective glass transitions of the components. These are compared with the “macroscopic” counterparts disentangled by the analysis of the DSC results in terms of a model based on the effects of thermally driven concentration fluctuations and self-concentration. At the microscopic level, the mixtures are dynamically heterogeneous for blends with intermediate concentrations or rich in PS, while the sample with highest content of the fast SBR component looks as dynamically homogeneous. Moreover, the combination of SANS and DSC has allowed determining the relevant length scale for the α-relaxation through its loss of equilibrium to be ≈30 Å. This is compared with the different characteristic length scales that can be identified in these complex mixtures from structural, thermodynamical, and dynamical points of view because of the combined approach followed. We also discuss the sources of the non-Gaussian effects observed for the atomic displacements and the applicability of a Lindemann-like criterion in these materials.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/60946
url http://hdl.handle.net/10810/60946
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MICINN/PID2021-123438NB-I00/
https://pubs.acs.org/doi/10.1021/acs.macromol.2c02368
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/3.0/es/
Atribución 3.0 España
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/3.0/es/
Atribución 3.0 España
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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