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
- Institución
- Universidad Tecnológica Nacional
- OAI Identificador
- oai:ria.utn.edu.ar:20.500.12272/3108
Ver los metadatos del registro completo
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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 Nacional2025-09-29T14:29:40Zoai: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:a2025-09-29 14:29:40.341Repositorio 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 |
12.559606 |