Quantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions

Handle URI:
http://hdl.handle.net/10754/609003
Title:
Quantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions
Authors:
Rai, Durgesh K.; Beaucage, Gregory; Ratkanthwar, Kedar ( 0000-0002-6324-696X ) ; Beaucage, Peter; Ramachandran, Ramnath; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 )
Abstract:
Mass fractal scaling, reflected in the mass fractal dimension df, is independently impacted by topology, reflected in the connectivity dimension c, and by tortuosity, reflected in the minimum dimension dmin. The mass fractal dimension is related to these other dimensions by df=cdmin. Branched fractal structures have a higher mass fractal dimension compared to linear structures due to a higher c, and extended structures have a lower dimension compared to convoluted self-avoiding and Gaussian walks due to a lower dmin. It is found, in this work, that macromolecules in thermodynamic equilibrium display a fixed mass fractal dimension df under good solvent conditions, regardless of chain topology. These equilibrium structures accommodate changes in chain topology such as branching c by a decrease in chain tortuosity dmin. Symmetric star polymers are used to understand the structure of complex macromolecular topologies. A recently published hybrid Unified scattering function accounts for interarm correlations in symmetric star polymers along with polymer-solvent interaction for chains of arbitrary scaling dimension. Dilute solutions of linear, three-arm and six-arm polyisoprene stars are studied under good solvent conditions in deuterated p-xylene. Reduced chain tortuosity can be viewed as steric straightening of the arms. Steric effects for star topologies are quantified, and it is found that steric straightening of arms is more significant for lower-molecular-weight arms. The observation of constant df is explained through a modification of Flory-Krigbaum theory for branched polymers.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Quantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions 2016, 93 (5) Physical Review E
Publisher:
American Physical Society (APS)
Journal:
Physical Review E
Issue Date:
5-May-2016
DOI:
10.1103/PhysRevE.93.052501
Type:
Article
ISSN:
2470-0045; 2470-0053
Additional Links:
http://link.aps.org/doi/10.1103/PhysRevE.93.052501
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorRai, Durgesh K.en
dc.contributor.authorBeaucage, Gregoryen
dc.contributor.authorRatkanthwar, Kedaren
dc.contributor.authorBeaucage, Peteren
dc.contributor.authorRamachandran, Ramnathen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.date.accessioned2016-05-11T07:29:17Zen
dc.date.available2016-05-11T07:29:17Zen
dc.date.issued2016-05-05en
dc.identifier.citationQuantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions 2016, 93 (5) Physical Review Een
dc.identifier.issn2470-0045en
dc.identifier.issn2470-0053en
dc.identifier.doi10.1103/PhysRevE.93.052501en
dc.identifier.urihttp://hdl.handle.net/10754/609003en
dc.description.abstractMass fractal scaling, reflected in the mass fractal dimension df, is independently impacted by topology, reflected in the connectivity dimension c, and by tortuosity, reflected in the minimum dimension dmin. The mass fractal dimension is related to these other dimensions by df=cdmin. Branched fractal structures have a higher mass fractal dimension compared to linear structures due to a higher c, and extended structures have a lower dimension compared to convoluted self-avoiding and Gaussian walks due to a lower dmin. It is found, in this work, that macromolecules in thermodynamic equilibrium display a fixed mass fractal dimension df under good solvent conditions, regardless of chain topology. These equilibrium structures accommodate changes in chain topology such as branching c by a decrease in chain tortuosity dmin. Symmetric star polymers are used to understand the structure of complex macromolecular topologies. A recently published hybrid Unified scattering function accounts for interarm correlations in symmetric star polymers along with polymer-solvent interaction for chains of arbitrary scaling dimension. Dilute solutions of linear, three-arm and six-arm polyisoprene stars are studied under good solvent conditions in deuterated p-xylene. Reduced chain tortuosity can be viewed as steric straightening of the arms. Steric effects for star topologies are quantified, and it is found that steric straightening of arms is more significant for lower-molecular-weight arms. The observation of constant df is explained through a modification of Flory-Krigbaum theory for branched polymers.en
dc.language.isoenen
dc.publisherAmerican Physical Society (APS)en
dc.relation.urlhttp://link.aps.org/doi/10.1103/PhysRevE.93.052501en
dc.rightsArchived with thanks to Physical Review Een
dc.titleQuantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditionsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalPhysical Review Een
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionBiology and Soft Matter Division, Oak Ridge National Laboratory, P.O. Box 2008, MS-6454 Oak Ridge, Tennessee 37831, USAen
dc.contributor.institutionMaterials Science and Engineering, University of Cincinnati, 492 Rhodes Hall, Cincinnati, Ohio 45221, USAen
dc.contributor.institutionDepartment of Chemistry, University of Athens, Panepistimiopolis, Zografou 15771, Athens, Greeceen
dc.contributor.institutionDepartment of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, USAen
dc.contributor.institutionProcter & Gamble, 1 P&G Plaza, Cincinnati, Ohio 45202, USAen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorRatkanthwar, Kedaren
kaust.authorHadjichristidis, Nikolaosen
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