Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

Handle URI:
http://hdl.handle.net/10754/625597
Title:
Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains
Authors:
Shivokhin, Maksim E. ( 0000-0003-3725-9959 ) ; Read, Daniel J.; Kouloumasis, Dimitris; Kocen, Rok; Zhuge, Flanco; Bailly, Christian; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Likhtman, Alexei E.
Abstract:
We propose and verify methods based on the slip-spring (SSp) model [ Macromolecules 2005, 38, 14 ] for predicting the effect of any monodisperse, binary, or ternary environment of topological constraints on the relaxation of the end-to-end vector of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We also report the synthesis of new binary and ternary polybutadiene systems, the measurement of their linear viscoelastic response, and the prediction of these data by the SSp model. We next clarify the relaxation mechanisms of probe chains in these constraint release (CR) environments by analyzing a set of "toy" SSp models with simplified constraint release rates, by examining fluctuations of the end-to-end vector. In our analysis, the longest relaxation time of the probe chain is determined by a competition between the longest relaxation times of the effective CR motions of the fat and thin tubes and the motion of the chain itself in the thin tube. This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe's end-to-end vector in polydisperse systems. We follow the CR picture of Viovy et al. [ Macromolecules 1991, 24, 3587 ] and refine the effective chain friction in the thin and fat tubes based on Read et al. [ J. Rheol. 2012, 56, 823 ]. The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers. The consistency between the SSp model and tube model predictions is a strong indicator of the compatibility between these two distinct mesoscopic frameworks.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Polymer Synthesis Laboratory
Citation:
Shivokhin ME, Read DJ, Kouloumasis D, Kocen R, Zhuge F, et al. (2017) Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains. Macromolecules 50: 4501–4523. Available: http://dx.doi.org/10.1021/acs.macromol.6b01947.
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
30-May-2017
DOI:
10.1021/acs.macromol.6b01947
Type:
Article
ISSN:
0024-9297; 1520-5835
Sponsors:
We thank Dietmar Auhl and Hiroshi Watanabe for kindly supplying experimental data of
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.macromol.6b01947
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorShivokhin, Maksim E.en
dc.contributor.authorRead, Daniel J.en
dc.contributor.authorKouloumasis, Dimitrisen
dc.contributor.authorKocen, Roken
dc.contributor.authorZhuge, Flancoen
dc.contributor.authorBailly, Christianen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorLikhtman, Alexei E.en
dc.date.accessioned2017-10-03T12:49:28Z-
dc.date.available2017-10-03T12:49:28Z-
dc.date.issued2017-05-30en
dc.identifier.citationShivokhin ME, Read DJ, Kouloumasis D, Kocen R, Zhuge F, et al. (2017) Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains. Macromolecules 50: 4501–4523. Available: http://dx.doi.org/10.1021/acs.macromol.6b01947.en
dc.identifier.issn0024-9297en
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/acs.macromol.6b01947en
dc.identifier.urihttp://hdl.handle.net/10754/625597-
dc.description.abstractWe propose and verify methods based on the slip-spring (SSp) model [ Macromolecules 2005, 38, 14 ] for predicting the effect of any monodisperse, binary, or ternary environment of topological constraints on the relaxation of the end-to-end vector of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We also report the synthesis of new binary and ternary polybutadiene systems, the measurement of their linear viscoelastic response, and the prediction of these data by the SSp model. We next clarify the relaxation mechanisms of probe chains in these constraint release (CR) environments by analyzing a set of "toy" SSp models with simplified constraint release rates, by examining fluctuations of the end-to-end vector. In our analysis, the longest relaxation time of the probe chain is determined by a competition between the longest relaxation times of the effective CR motions of the fat and thin tubes and the motion of the chain itself in the thin tube. This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe's end-to-end vector in polydisperse systems. We follow the CR picture of Viovy et al. [ Macromolecules 1991, 24, 3587 ] and refine the effective chain friction in the thin and fat tubes based on Read et al. [ J. Rheol. 2012, 56, 823 ]. The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers. The consistency between the SSp model and tube model predictions is a strong indicator of the compatibility between these two distinct mesoscopic frameworks.en
dc.description.sponsorshipWe thank Dietmar Auhl and Hiroshi Watanabe for kindly supplying experimental data ofen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.macromol.6b01947en
dc.titleUnderstanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chainsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionExxonMobil Chemical Company, Baytown Technology and Engineering Complex, 5200 Bayway Drive, Baytown, TX, , United Statesen
dc.contributor.institutionCenter for Molecular Study of Condensed Soft Matter, Department of Chemical and Biological Engineering, Illinois Institute of Technology, 3440 South Dearborn Street, Chicago, IL, 60616, , United Statesen
dc.contributor.institutionBio- and Soft Matter Division (BSMA), Institute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCL), Place Croix de Sud 1, Louvain-la-Neuve, 1348, , Belgiumen
dc.contributor.institutionSchool of Mathematics, University of Leeds, Leeds, LS2 9JT, , United Kingdomen
dc.contributor.institutionLaboratory of Industrial Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis Zografou 1, Athens, 57 71, , Greeceen
dc.contributor.institutionSchool of Mathematical and Physical Sciences, University of Reading, Reading, RG6 6AX, , United Kingdomen
kaust.authorHadjichristidis, Nikolaosen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.