Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching...

Autores
Vega, Jorge Rubén; Clementi, Luis Alberto; Meira, Gregorio
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión aceptada
Descripción
This article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a polymer with tetrafunctional branch units has been calculated with the Stockmayer equation (1943); and an ideal SEC analysis has been simulated that assumes u-solvent, perfect measurements, and perfect fractionation by hydrodynamic volume except for a minor mixing in the detector cells. In ideal SEC, a negligible bias is introduced into the MMD, with the local dispersity exhibiting a maximum of 1.0035 at the high molar masses. This result is consistent with previous theoretical investigations, but differs qualitatively from experimental observationsofpolymerscontainingshort-andlong-chain branches. When including band broadening in the columns while still assuming perfect measurements, the MMDremainsessentiallyunbiased.Incontrast,poorMMD estimates are obtained when the chromatograms are contaminated with additive noise. Only qualitative estimates of the LCBD are possible, due to theoretical limitations combined with propagation of errors in a highly nonlinear calculation procedure.
Fil: Vega, Jorge Rubén. Universidad Tecnológica Nacional. Facultad Regional Santa Fe, Argentina.
Fil: Clementi, Luis Alberto. Universidad Tecnológica Nacional. Facultad Regional Santa Fe, Argentina.
Fil: Meira, Gregorio. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.
Fil: Vega, Jorge Rubén. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.
Fil: Clementi, Luis Alberto. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.
Peer Reviewed
Materia
Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/3108
Acceder
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network_name_str Repositorio Institucional Abierto (UTN)
spelling Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degreeVega, Jorge RubénClementi, Luis AlbertoMeira, GregorioRandomly-Branched PolymersDistribution of 5 Molar MassBranching DegreeaThis article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a polymer with tetrafunctional branch units has been calculated with the Stockmayer equation (1943); and an ideal SEC analysis has been simulated that assumes u-solvent, perfect measurements, and perfect fractionation by hydrodynamic volume except for a minor mixing in the detector cells. In ideal SEC, a negligible bias is introduced into the MMD, with the local dispersity exhibiting a maximum of 1.0035 at the high molar masses. This result is consistent with previous theoretical investigations, but differs qualitatively from experimental observationsofpolymerscontainingshort-andlong-chain branches. When including band broadening in the columns while still assuming perfect measurements, the MMDremainsessentiallyunbiased.Incontrast,poorMMD estimates are obtained when the chromatograms are contaminated with additive noise. Only qualitative estimates of the LCBD are possible, due to theoretical limitations combined with propagation of errors in a highly nonlinear calculation procedure.Fil: Vega, Jorge Rubén. Universidad Tecnológica Nacional. Facultad Regional Santa Fe, Argentina.Fil: Clementi, Luis Alberto. Universidad Tecnológica Nacional. Facultad Regional Santa Fe, Argentina.Fil: Meira, Gregorio. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.Fil: Vega, Jorge Rubén. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.Fil: Clementi, Luis Alberto. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.Peer Reviewed2018-09-11T20:06:33Z2018-09-11T20:06:33Z2013info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfMacromolecular Theory And Simulations, 23(2), pp. 90-100 (2013)http://hdl.handle.net/20.500.12272/3108engTecnicas numéricas de estimación y optimización: aplicaciones en problemas de nanotecnología y de energía eléctrica - Código: 25/0147info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Condiciones de Uso desde su aprobaciónAtribución-NoComercial-CompartirIgual 4.0 Internacionalreponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2025-10-23T11:18:43Zoai:ria.utn.edu.ar:20.500.12272/3108instacron:UTNInstitucionalhttp://ria.utn.edu.ar/Universidad públicaNo correspondehttp://ria.utn.edu.ar/oaigestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:a2025-10-23 11:18:43.652Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
spellingShingle Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
Vega, Jorge Rubén
Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
title_short Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_full Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_fullStr Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_full_unstemmed Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
title_sort Randomly-branched polymers by size exclusion chromatography with triple detection : computer simulation study for estimating errors in the distribution of molar mass and branching degree
dc.creator.none.fl_str_mv Vega, Jorge Rubén
Clementi, Luis Alberto
Meira, Gregorio
author Vega, Jorge Rubén
author_facet Vega, Jorge Rubén
Clementi, Luis Alberto
Meira, Gregorio
author_role author
author2 Clementi, Luis Alberto
Meira, Gregorio
author2_role author
author
dc.subject.none.fl_str_mv Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
topic Randomly-Branched Polymers
Distribution of 5 Molar Mass
Branching Degreea
dc.description.none.fl_txt_mv This article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a polymer with tetrafunctional branch units has been calculated with the Stockmayer equation (1943); and an ideal SEC analysis has been simulated that assumes u-solvent, perfect measurements, and perfect fractionation by hydrodynamic volume except for a minor mixing in the detector cells. In ideal SEC, a negligible bias is introduced into the MMD, with the local dispersity exhibiting a maximum of 1.0035 at the high molar masses. This result is consistent with previous theoretical investigations, but differs qualitatively from experimental observationsofpolymerscontainingshort-andlong-chain branches. When including band broadening in the columns while still assuming perfect measurements, the MMDremainsessentiallyunbiased.Incontrast,poorMMD estimates are obtained when the chromatograms are contaminated with additive noise. Only qualitative estimates of the LCBD are possible, due to theoretical limitations combined with propagation of errors in a highly nonlinear calculation procedure.
Fil: Vega, Jorge Rubén. Universidad Tecnológica Nacional. Facultad Regional Santa Fe, Argentina.
Fil: Clementi, Luis Alberto. Universidad Tecnológica Nacional. Facultad Regional Santa Fe, Argentina.
Fil: Meira, Gregorio. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.
Fil: Vega, Jorge Rubén. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.
Fil: Clementi, Luis Alberto. CONICET-Universidad Nacional del Litoral. INTEC; Argentina.
Peer Reviewed
description This article theoretically evaluates the biases introduced into the distributions of molar masses (MMD) and the number of long chain branches per molecule (LCBD), when randomly-branched polymers are analyzed by size exclusion chromatography (SEC) with molar mass-sensitive detectors. The MMD of a polymer with tetrafunctional branch units has been calculated with the Stockmayer equation (1943); and an ideal SEC analysis has been simulated that assumes u-solvent, perfect measurements, and perfect fractionation by hydrodynamic volume except for a minor mixing in the detector cells. In ideal SEC, a negligible bias is introduced into the MMD, with the local dispersity exhibiting a maximum of 1.0035 at the high molar masses. This result is consistent with previous theoretical investigations, but differs qualitatively from experimental observationsofpolymerscontainingshort-andlong-chain branches. When including band broadening in the columns while still assuming perfect measurements, the MMDremainsessentiallyunbiased.Incontrast,poorMMD estimates are obtained when the chromatograms are contaminated with additive noise. Only qualitative estimates of the LCBD are possible, due to theoretical limitations combined with propagation of errors in a highly nonlinear calculation procedure.
publishDate 2013
dc.date.none.fl_str_mv 2013
2018-09-11T20:06:33Z
2018-09-11T20:06:33Z
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv Macromolecular Theory And Simulations, 23(2), pp. 90-100 (2013)
http://hdl.handle.net/20.500.12272/3108
identifier_str_mv Macromolecular Theory And Simulations, 23(2), pp. 90-100 (2013)
url http://hdl.handle.net/20.500.12272/3108
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Tecnicas numéricas de estimación y optimización: aplicaciones en problemas de nanotecnología y de energía eléctrica - Código: 25/0147
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Condiciones de Uso desde su aprobación
Atribución-NoComercial-CompartirIgual 4.0 Internacional
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Condiciones de Uso desde su aprobación
Atribución-NoComercial-CompartirIgual 4.0 Internacional
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.source.none.fl_str_mv reponame:Repositorio Institucional Abierto (UTN)
instname:Universidad Tecnológica Nacional
reponame_str Repositorio Institucional Abierto (UTN)
collection Repositorio Institucional Abierto (UTN)
instname_str Universidad Tecnológica Nacional
repository.name.fl_str_mv Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacional
repository.mail.fl_str_mv gestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.ar
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score 12.471625

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