Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers

Unformatted post-print version of the accepted article

Bibliographic Details
Authors: Safari, Maryam, Leon Boigues, Laia, Shi, Guangyu, Maiz, Jon, Liu, Guoming, Wang, Dujin, Mijangos, Carmen, Müller Sánchez, Alejandro Jesús
Format: article
Publication Date:2020
Country:España
Institution:Universidad del País Vasco
Repository:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/50780
Online Access:http://hdl.handle.net/10810/50780
Access Level:Open access
Keyword:biocopolyesters
confinement
isodimorphism
homogeneous nucleation
crystallization
genetics
copolymers
homopolymers
nucleation
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oai_identifier_str oai:addi.ehu.eus:10810/50780
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
title Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
spellingShingle Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
Safari, Maryam
biocopolyesters
confinement
isodimorphism
homogeneous nucleation
crystallization
genetics
copolymers
homopolymers
nucleation
title_short Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
title_full Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
title_fullStr Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
title_full_unstemmed Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
title_sort Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random Copolymers
dc.creator.none.fl_str_mv Safari, Maryam
Leon Boigues, Laia
Shi, Guangyu
Maiz, Jon
Liu, Guoming
Wang, Dujin
Mijangos, Carmen
Müller Sánchez, Alejandro Jesús
author Safari, Maryam
author_facet Safari, Maryam
Leon Boigues, Laia
Shi, Guangyu
Maiz, Jon
Liu, Guoming
Wang, Dujin
Mijangos, Carmen
Müller Sánchez, Alejandro Jesús
author_role author
author2 Leon Boigues, Laia
Shi, Guangyu
Maiz, Jon
Liu, Guoming
Wang, Dujin
Mijangos, Carmen
Müller Sánchez, Alejandro Jesús
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
dc.subject.none.fl_str_mv biocopolyesters
confinement
isodimorphism
homogeneous nucleation
crystallization
genetics
copolymers
homopolymers
nucleation
topic biocopolyesters
confinement
isodimorphism
homogeneous nucleation
crystallization
genetics
copolymers
homopolymers
nucleation
description Unformatted post-print version of the accepted article
publishDate 2020
dc.date.none.fl_str_mv 2020
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/50780
url http://hdl.handle.net/10810/50780
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/H2020/778092
info:eu-repo/grantAgreement/MCIU/MAT2017-83014-C2-2-P/
info:eu-repo/grantAgreement/MCIU/MAT2017-83014-C2-1-P/
https://pubs.acs.org/doi/10.1021/acs.macromol.0c01081
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
Copyright © 2020 American Chemical Society
eu_rights_str_mv openAccess
rights_invalid_str_mv Copyright © 2020 American Chemical Society
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
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
_version_ 1869419568340926464
spelling Effect of Nanoconfinement on the isodimorphic crystallization of Poly(butylene succinate-ran-caprolactone) Random CopolymersSafari, MaryamLeon Boigues, LaiaShi, GuangyuMaiz, JonLiu, GuomingWang, DujinMijangos, CarmenMüller Sánchez, Alejandro Jesúsbiocopolyestersconfinementisodimorphismhomogeneous nucleationcrystallizationgeneticscopolymershomopolymersnucleationUnformatted post-print version of the accepted articleIn this paper, we study for the first time the effect of hard confinement on the isodimorphic crystallization of random copolyesters. A series of poly(butylene succinate-ran-caprolactone) samples encompassing the entire composition range were successfully infiltrated into nanoporous alumina templates (AAO) with a fixed diameter of 100 nm. Samples were characterized using scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and grazing-incidence wide-angle X-ray diffraction (GIWAXS). FTIR proved that PBS-rich nanofibers showed interactions between the copolyester chains and the walls of the AAO templates; however, the PCL-rich nanofibers did not show any interaction with the AAO walls. All infiltrated samples experienced a very large decrease in crystallization temperature, as expected, since the level of confinement is large enough to suppress heterogeneous nucleation. In spite of this, all copolymers were able to crystallize, regardless of composition. Additionally, when Tc or Tm are plotted versus copolymer composition a clear pseudo-eutectic point is observed. These results indicate that the isodimorphic behavior of the copolyesters is maintained under hard confinement. Infiltrated PCL undergoes homogeneous nucleation (inside the nanopore volume) as expected by the lack of interaction with the AAO walls. On the other hand, PBS exhibited a surface nucleation mechanism triggered by the interactions with the AAO walls. In the case of random copolymers, all PCL-rich copolymers nucleated homogeneously. However, in the case of PBS-rich copolymers, the nucleation gradually changed from surface-induced nucleation for neat PBS to homogeneous nucleation, as PCL concentration in the copolymers increased and the interactions of PBS chains with the AAO walls are diluted. The confinement under 100 nm nanopores did not change the orientation of the PBS or PCL phase crystals, which kept their chain direction perpendicular to the pore axis, as demonstrated by GIWAXS.We acknowledge the support of the National Key R&D Program of China (2017YFE0117800), the National Natural Science Foundation of China (21873109, 51820105005). We would also like to thank the financial support provided by the BIODEST project; this project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 778092. The UPV/EHU and ICTP-CSIC Institutions acknowledge financial support from the Spanish Ministry of Science, Innovation, and Universities (MAT2017-83014-C2-2-P and MAT2017-83014-C2-1-P). M.S. thankfully acknowledges her Ph.D. fellowship by POLYMAT Basque Center for Macromolecular Design and Engineering. Authors would like to thank Dr. Antxon Martinez de Ilarduya and Prof. Sebastian Muñoz for their help in the synthesis of copolyesters at UPC, Spain. J.M. gratefully acknowledges support from the Provincial Council of Gipuzkoa under the program Fellow Gipuzkoa and “Fomento San Sebastián” in the framework program “Retorno del Talento Local” Donostia up! 2016.ACSEuropean Commission202120212020info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/50780reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/EC/H2020/778092info:eu-repo/grantAgreement/MCIU/MAT2017-83014-C2-2-P/info:eu-repo/grantAgreement/MCIU/MAT2017-83014-C2-1-P/https://pubs.acs.org/doi/10.1021/acs.macromol.0c01081info:eu-repo/semantics/openAccessCopyright © 2020 American Chemical Societyoai:addi.ehu.eus:10810/507802026-06-18T09:23:17Z
score 15,300719

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