Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics

Autores
Taverna, María Eugenia; Altorbaq, Abdullah S.; Kumar, Sanat K.; Olmedo Martínez, Jorge L.; Busatto, Carlos Alberto; Zubitur, Manuela; Mugica, Agurtzane; Nicolau, Verónica V.; Estenoz, Diana Alejandra; Müller, Alejandro J.
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime.
Fil: Taverna, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Altorbaq, Abdullah S.. Columbia University; Estados Unidos
Fil: Kumar, Sanat K.. Columbia University; Estados Unidos
Fil: Olmedo Martínez, Jorge L.. Universidad del Pais Vasco. Polymat.; España
Fil: Busatto, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Zubitur, Manuela. Universidad del Pais Vasco. Polymat.; España
Fil: Mugica, Agurtzane. Universidad del Pais Vasco. Polymat.; España
Fil: Nicolau, Verónica V.. Universidad Tecnológica Nacional; Argentina
Fil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Müller, Alejandro J.. Universidad del Pais Vasco. Polymat.; España
Materia
BIOPOLYMER
CRYSTALLIZATION
KINETICS
NANOCOMPOSITES
NUCLEATION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/217741
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/217741
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization KineticsTaverna, María EugeniaAltorbaq, Abdullah S.Kumar, Sanat K.Olmedo Martínez, Jorge L.Busatto, Carlos AlbertoZubitur, ManuelaMugica, AgurtzaneNicolau, Verónica V.Estenoz, Diana AlejandraMüller, Alejandro J.BIOPOLYMERCRYSTALLIZATIONKINETICSNANOCOMPOSITESNUCLEATIONhttps://purl.org/becyt/ford/2.10https://purl.org/becyt/ford/2The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime.Fil: Taverna, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Altorbaq, Abdullah S.. Columbia University; Estados UnidosFil: Kumar, Sanat K.. Columbia University; Estados UnidosFil: Olmedo Martínez, Jorge L.. Universidad del Pais Vasco. Polymat.; EspañaFil: Busatto, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Zubitur, Manuela. Universidad del Pais Vasco. Polymat.; EspañaFil: Mugica, Agurtzane. Universidad del Pais Vasco. Polymat.; EspañaFil: Nicolau, Verónica V.. Universidad Tecnológica Nacional; ArgentinaFil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Müller, Alejandro J.. Universidad del Pais Vasco. Polymat.; EspañaAmerican Chemical Society2022-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/217741Taverna, María Eugenia; Altorbaq, Abdullah S.; Kumar, Sanat K.; Olmedo Martínez, Jorge L.; Busatto, Carlos Alberto; et al.; Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics; American Chemical Society; Macromolecules; 55; 17; 8-2022; 7663-76730024-9297CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.macromol.2c00925info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.macromol.2c00925info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:23:59Zoai:ri.conicet.gov.ar:11336/217741instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-10 13:23:59.836CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
title Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
spellingShingle Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
Taverna, María Eugenia
BIOPOLYMER
CRYSTALLIZATION
KINETICS
NANOCOMPOSITES
NUCLEATION
title_short Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
title_full Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
title_fullStr Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
title_full_unstemmed Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
title_sort Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics
dc.creator.none.fl_str_mv Taverna, María Eugenia
Altorbaq, Abdullah S.
Kumar, Sanat K.
Olmedo Martínez, Jorge L.
Busatto, Carlos Alberto
Zubitur, Manuela
Mugica, Agurtzane
Nicolau, Verónica V.
Estenoz, Diana Alejandra
Müller, Alejandro J.
author Taverna, María Eugenia
author_facet Taverna, María Eugenia
Altorbaq, Abdullah S.
Kumar, Sanat K.
Olmedo Martínez, Jorge L.
Busatto, Carlos Alberto
Zubitur, Manuela
Mugica, Agurtzane
Nicolau, Verónica V.
Estenoz, Diana Alejandra
Müller, Alejandro J.
author_role author
author2 Altorbaq, Abdullah S.
Kumar, Sanat K.
Olmedo Martínez, Jorge L.
Busatto, Carlos Alberto
Zubitur, Manuela
Mugica, Agurtzane
Nicolau, Verónica V.
Estenoz, Diana Alejandra
Müller, Alejandro J.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv BIOPOLYMER
CRYSTALLIZATION
KINETICS
NANOCOMPOSITES
NUCLEATION
topic BIOPOLYMER
CRYSTALLIZATION
KINETICS
NANOCOMPOSITES
NUCLEATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime.
Fil: Taverna, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Altorbaq, Abdullah S.. Columbia University; Estados Unidos
Fil: Kumar, Sanat K.. Columbia University; Estados Unidos
Fil: Olmedo Martínez, Jorge L.. Universidad del Pais Vasco. Polymat.; España
Fil: Busatto, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Zubitur, Manuela. Universidad del Pais Vasco. Polymat.; España
Fil: Mugica, Agurtzane. Universidad del Pais Vasco. Polymat.; España
Fil: Nicolau, Verónica V.. Universidad Tecnológica Nacional; Argentina
Fil: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Müller, Alejandro J.. Universidad del Pais Vasco. Polymat.; España
description The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime.
publishDate 2022
dc.date.none.fl_str_mv 2022-08
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/217741
Taverna, María Eugenia; Altorbaq, Abdullah S.; Kumar, Sanat K.; Olmedo Martínez, Jorge L.; Busatto, Carlos Alberto; et al.; Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics; American Chemical Society; Macromolecules; 55; 17; 8-2022; 7663-7673
0024-9297
CONICET Digital
CONICET
url http://hdl.handle.net/11336/217741
identifier_str_mv Taverna, María Eugenia; Altorbaq, Abdullah S.; Kumar, Sanat K.; Olmedo Martínez, Jorge L.; Busatto, Carlos Alberto; et al.; Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics; American Chemical Society; Macromolecules; 55; 17; 8-2022; 7663-7673
0024-9297
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.macromol.2c00925
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.macromol.2c00925
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
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:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.48226

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