Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion

In this study, the dynamic viscoelastic properties of three structurally modified poly(lactic acid) (PLA) samples processed through reactive extrusion (REX) were analyzed. While classical chromatographic and spectroscopic techniques exhibited limited sensitivity to the presence of topological change...

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Detalles Bibliográficos
Autores: Cailloux, Jonathan, Santana Pérez, Orlando O., Maspoch, Maria Lluïsa, Bou, Jordi J., Carrasco, Félix
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/12379
Acceso en línea:http://hdl.handle.net/10256/12379
Access Level:acceso abierto
Palabra clave:Reologia
Rheology
Polímers -- Reologia
Polymers -- Rheology
Viscoelasticitat
Viscoelasticity
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spelling Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusionCailloux, JonathanSantana Pérez, Orlando O.Maspoch, Maria LluïsaBou, Jordi J.Carrasco, FélixReologiaRheologyPolímers -- ReologiaPolymers -- RheologyViscoelasticitatViscoelasticityIn this study, the dynamic viscoelastic properties of three structurally modified poly(lactic acid) (PLA) samples processed through reactive extrusion (REX) were analyzed. While classical chromatographic and spectroscopic techniques exhibited limited sensitivity to the presence of topological changes, rheological measurements confirmed the presence of nonuniform branched macromolecules, holding sparsely long chain branches. According to the processing conditions used, the flow activation energy and the thermorheologically simple behavior remained roughly unaffected for PLA-REX containing an amount of modified chains up to 24%. Distinctly separated relaxation processes in a broader transition zone were observed in the complex viscosity function (|η∗(ω)|) of all PLA-REX samples. The "extended Carreau-Yassuda" model and an extension of the Havriliak-Negami model, proposed in this work, were used to capture the main characteristics of |η ∗ (ω)| experimental data. Both fitted models were inverted to molecular weight distribution (MWD) spectrum using the numerical inversion technique of Shaw and Tuminello, and these were compared with size exclusion chromatography MWDs. It was shown that the resolution of the predicted bimodal MWDs was enhanced when the model used to fit |η ∗ (ω)| data was exempted from the Cox-Merz rule and included a complex time dependence. Based on the MWDs deduced from solely melt measurements, a procedure was described to quantitatively estimate the amount of modified chainsThe authors would like to acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness through the Project MAT2013-40730-P. BASF is thanked for kindly supplying the reactive agent and Irganox 1010The authors would like to acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness through the Project MAT2013-40730-PAmerican Institute of Physics (AIP)2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10256/12379© Journal of Rheology, 2015, vol. 59, núm. 5, p. 1191-1227Articles publicats (D-EQATA)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1122/1.4928071info:eu-repo/semantics/altIdentifier/issn/0148-6055info:eu-repo/semantics/altIdentifier/eissn/1520-8516Tots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/123792026-05-29T05:05:01Z
dc.title.none.fl_str_mv Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
title Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
spellingShingle Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
Cailloux, Jonathan
Reologia
Rheology
Polímers -- Reologia
Polymers -- Rheology
Viscoelasticitat
Viscoelasticity
title_short Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
title_full Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
title_fullStr Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
title_full_unstemmed Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
title_sort Using viscoelastic properties to quantitatively estimate the amount of modified poly(lactic acid) chains through reactive extrusion
dc.creator.none.fl_str_mv Cailloux, Jonathan
Santana Pérez, Orlando O.
Maspoch, Maria Lluïsa
Bou, Jordi J.
Carrasco, Félix
author Cailloux, Jonathan
author_facet Cailloux, Jonathan
Santana Pérez, Orlando O.
Maspoch, Maria Lluïsa
Bou, Jordi J.
Carrasco, Félix
author_role author
author2 Santana Pérez, Orlando O.
Maspoch, Maria Lluïsa
Bou, Jordi J.
Carrasco, Félix
author2_role author
author
author
author
dc.subject.none.fl_str_mv Reologia
Rheology
Polímers -- Reologia
Polymers -- Rheology
Viscoelasticitat
Viscoelasticity
topic Reologia
Rheology
Polímers -- Reologia
Polymers -- Rheology
Viscoelasticitat
Viscoelasticity
description In this study, the dynamic viscoelastic properties of three structurally modified poly(lactic acid) (PLA) samples processed through reactive extrusion (REX) were analyzed. While classical chromatographic and spectroscopic techniques exhibited limited sensitivity to the presence of topological changes, rheological measurements confirmed the presence of nonuniform branched macromolecules, holding sparsely long chain branches. According to the processing conditions used, the flow activation energy and the thermorheologically simple behavior remained roughly unaffected for PLA-REX containing an amount of modified chains up to 24%. Distinctly separated relaxation processes in a broader transition zone were observed in the complex viscosity function (|η∗(ω)|) of all PLA-REX samples. The "extended Carreau-Yassuda" model and an extension of the Havriliak-Negami model, proposed in this work, were used to capture the main characteristics of |η ∗ (ω)| experimental data. Both fitted models were inverted to molecular weight distribution (MWD) spectrum using the numerical inversion technique of Shaw and Tuminello, and these were compared with size exclusion chromatography MWDs. It was shown that the resolution of the predicted bimodal MWDs was enhanced when the model used to fit |η ∗ (ω)| data was exempted from the Cox-Merz rule and included a complex time dependence. Based on the MWDs deduced from solely melt measurements, a procedure was described to quantitatively estimate the amount of modified chains
publishDate 2015
dc.date.none.fl_str_mv 2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/12379
url http://hdl.handle.net/10256/12379
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1122/1.4928071
info:eu-repo/semantics/altIdentifier/issn/0148-6055
info:eu-repo/semantics/altIdentifier/eissn/1520-8516
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics (AIP)
publisher.none.fl_str_mv American Institute of Physics (AIP)
dc.source.none.fl_str_mv © Journal of Rheology, 2015, vol. 59, núm. 5, p. 1191-1227
Articles publicats (D-EQATA)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.198674

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