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Title: A multichain polymer slip-spring model with fluctuating number of entanglements for linear and nonlinear rheology

Abstract

A theoretically informed entangled polymer simulation approach is presented for description of the linear and non-linear rheology of entangled polymer melts. The approach relies on a many-chain representation and introduces the topological effects that arise from the non-crossability of molecules through effective fluctuating interactions, mediated by slip-springs, between neighboring pairs of macromolecules. The total number of slip-springs is not preserved but, instead, it is controlled through a chemical potential that determines the average molecular weight between entanglements. The behavior of the model is discussed in the context of a recent theory for description of homogeneous materials, and its relevance is established by comparing its predictions to experimental linear and non-linear rheology data for a series of well-characterized linear polyisoprene melts. The results are shown to be in quantitative agreement with experiment and suggest that the proposed formalism may also be used to describe the dynamics of inhomogeneous systems, such as composites and copolymers. Importantly, the fundamental connection made here between our many-chain model and the well-established, thermodynamically consistent single-chain mean-field models provides a path to systematic coarse-graining for prediction of polymer rheology in structurally homogeneous and heterogeneous materials.

Authors:
;  [1]; ;
  1. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439 (United States)
Publication Date:
OSTI Identifier:
22493385
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPARATIVE EVALUATIONS; COMPUTERIZED SIMULATION; COPOLYMERS; MEAN-FIELD THEORY; MOLECULAR WEIGHT; MOLECULES; NONLINEAR PROBLEMS; POLYISOPRENE; POTENTIALS; RHEOLOGY; SLIP

Citation Formats

Ramírez-Hernández, Abelardo, Pablo, Juan J. de,, Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, Peters, Brandon L., Andreev, Marat, and Schieber, Jay D., E-mail: schieber@iit.edu. A multichain polymer slip-spring model with fluctuating number of entanglements for linear and nonlinear rheology. United States: N. p., 2015. Web. doi:10.1063/1.4936878.
Ramírez-Hernández, Abelardo, Pablo, Juan J. de,, Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, Peters, Brandon L., Andreev, Marat, & Schieber, Jay D., E-mail: schieber@iit.edu. A multichain polymer slip-spring model with fluctuating number of entanglements for linear and nonlinear rheology. United States. doi:10.1063/1.4936878.
Ramírez-Hernández, Abelardo, Pablo, Juan J. de,, Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, Peters, Brandon L., Andreev, Marat, and Schieber, Jay D., E-mail: schieber@iit.edu. Mon . "A multichain polymer slip-spring model with fluctuating number of entanglements for linear and nonlinear rheology". United States. doi:10.1063/1.4936878.
@article{osti_22493385,
title = {A multichain polymer slip-spring model with fluctuating number of entanglements for linear and nonlinear rheology},
author = {Ramírez-Hernández, Abelardo and Pablo, Juan J. de, and Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637 and Peters, Brandon L. and Andreev, Marat and Schieber, Jay D., E-mail: schieber@iit.edu},
abstractNote = {A theoretically informed entangled polymer simulation approach is presented for description of the linear and non-linear rheology of entangled polymer melts. The approach relies on a many-chain representation and introduces the topological effects that arise from the non-crossability of molecules through effective fluctuating interactions, mediated by slip-springs, between neighboring pairs of macromolecules. The total number of slip-springs is not preserved but, instead, it is controlled through a chemical potential that determines the average molecular weight between entanglements. The behavior of the model is discussed in the context of a recent theory for description of homogeneous materials, and its relevance is established by comparing its predictions to experimental linear and non-linear rheology data for a series of well-characterized linear polyisoprene melts. The results are shown to be in quantitative agreement with experiment and suggest that the proposed formalism may also be used to describe the dynamics of inhomogeneous systems, such as composites and copolymers. Importantly, the fundamental connection made here between our many-chain model and the well-established, thermodynamically consistent single-chain mean-field models provides a path to systematic coarse-graining for prediction of polymer rheology in structurally homogeneous and heterogeneous materials.},
doi = {10.1063/1.4936878},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 24,
volume = 143,
place = {United States},
year = {2015},
month = {12}
}

Works referencing / citing this record:

Modeling of Entangled Polymer Diffusion in Melts and Nanocomposites: A Review
journal, May 2019

  • Karatrantos, Argyrios; Composto, Russell J.; Winey, Karen I.
  • Polymers, Vol. 11, Issue 5
  • DOI: 10.3390/polym11050876