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. Furthermore, 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:

Ramírez-Hernández, Abelardo ^[1]; Peters, Brandon L. ^[2]; Andreev, Marat ^[2]; Schieber, Jay D. ^[3]; de Pablo, Juan J. ^[1]

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+ Show Author Affiliations

1. Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
2. The Univ. of Chicago, Chicago, IL (United States)
3. The Univ. of Chicago, Chicago, IL (United States); Illinois Inst. of Technology, Chicago, IL (United States)

Publication Date:

Tue Dec 15 00:00:00 EST 2015

Research Org.:

Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:

U.S. Army Research Laboratory, U.S. Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division; National Science Foundation (NSF)

OSTI Identifier:

1352831

Alternate Identifier(s):

OSTI ID: 1229791

Grant/Contract Number:  

AC02-06CH11357

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 143; Journal Issue: 24; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY