Understanding constraint release in star/linear polymer blends

Handle URI:
http://hdl.handle.net/10754/563492
Title:
Understanding constraint release in star/linear polymer blends
Authors:
Shivokhin, M. E.; Van Ruymbeke, Evelyne; Bailly, Christian M E; Kouloumasis, D.; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Likhtman, Alexei E.
Abstract:
In this paper, we exploit the stochastic slip-spring model to quantitatively predict the stress relaxation dynamics of star/linear blends with well-separated longest relaxation times and we analyze the results to assess the validity limits of the two main models describing the corresponding relaxation mechanisms within the framework of the tube picture (Doi's tube dilation and Viovy's constraint release by Rouse motions of the tube). Our main objective is to understand and model the stress relaxation function of the star component in the blend. To this end, we divide its relaxation function into three zones, each of them corresponding to a different dominating relaxation mechanism. After the initial fast Rouse motions, relaxation of the star is dominated at intermediate times by the "skinny" tube (made by all topological constraints) followed by exploration of the "fat" tube (made by long-lived obstacles only). At longer times, the tube dilation picture provides the right shape for the relaxation of the stars. However, the effect of short linear chains results in time-shift factors that have never been described before. On the basis of the analysis of the different friction coefficients involved in the relaxation of the star chains, we propose an equation predicting these time-shift factors. This allows us to develop an analytical equation combining all relaxation zones, which is verified by comparison with simulation results. © 2014 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Polymer Synthesis Laboratory
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
8-Apr-2014
DOI:
10.1021/ma402475a
Type:
Article
ISSN:
00249297
Sponsors:
We thank Dr. Dietmar Auhl for assistance in experimental part of this work and Prof. Hiroshi Watanabe, Dr. Zuowei Wang, Dr. Yuichi Masubuchi for valuable discussions. We also thank Prof. J. Roovers for providing us with experimental data of the monodisperse star polymers. The research leading to these results has received funding from the [European Community's] Seventh Framework Programme [FP7/2007-2013] under Grant Agreement No. 214627-DYNACOP. Computational resources have been provided by the supercomputing facilities of the Universite catholique de Louvain (CISM/UCL).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorShivokhin, M. E.en
dc.contributor.authorVan Ruymbeke, Evelyneen
dc.contributor.authorBailly, Christian M Een
dc.contributor.authorKouloumasis, D.en
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorLikhtman, Alexei E.en
dc.date.accessioned2015-08-03T11:52:47Zen
dc.date.available2015-08-03T11:52:47Zen
dc.date.issued2014-04-08en
dc.identifier.issn00249297en
dc.identifier.doi10.1021/ma402475aen
dc.identifier.urihttp://hdl.handle.net/10754/563492en
dc.description.abstractIn this paper, we exploit the stochastic slip-spring model to quantitatively predict the stress relaxation dynamics of star/linear blends with well-separated longest relaxation times and we analyze the results to assess the validity limits of the two main models describing the corresponding relaxation mechanisms within the framework of the tube picture (Doi's tube dilation and Viovy's constraint release by Rouse motions of the tube). Our main objective is to understand and model the stress relaxation function of the star component in the blend. To this end, we divide its relaxation function into three zones, each of them corresponding to a different dominating relaxation mechanism. After the initial fast Rouse motions, relaxation of the star is dominated at intermediate times by the "skinny" tube (made by all topological constraints) followed by exploration of the "fat" tube (made by long-lived obstacles only). At longer times, the tube dilation picture provides the right shape for the relaxation of the stars. However, the effect of short linear chains results in time-shift factors that have never been described before. On the basis of the analysis of the different friction coefficients involved in the relaxation of the star chains, we propose an equation predicting these time-shift factors. This allows us to develop an analytical equation combining all relaxation zones, which is verified by comparison with simulation results. © 2014 American Chemical Society.en
dc.description.sponsorshipWe thank Dr. Dietmar Auhl for assistance in experimental part of this work and Prof. Hiroshi Watanabe, Dr. Zuowei Wang, Dr. Yuichi Masubuchi for valuable discussions. We also thank Prof. J. Roovers for providing us with experimental data of the monodisperse star polymers. The research leading to these results has received funding from the [European Community's] Seventh Framework Programme [FP7/2007-2013] under Grant Agreement No. 214627-DYNACOP. Computational resources have been provided by the supercomputing facilities of the Universite catholique de Louvain (CISM/UCL).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleUnderstanding constraint release in star/linear polymer blendsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionDivision of Bio- and Soft Matter (BSMA), Institute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCL), Louvain-la-Neuve, Belgiumen
dc.contributor.institutionLaboratory of Industrial Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis Zografou, 157 71 Athens, Greeceen
dc.contributor.institutionSchool of Mathematical and Physical Sciences, University of Reading, Reading RG6 6AX, United Kingdomen
kaust.authorHadjichristidis, Nikolaosen
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