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Title: Stress Relaxation in Highly Oriented Melts of Entangled Polymers

Abstract

Here, molecular dynamics simulations are used to study relaxation of entangled polymer melts deformed far from equilibrium by uniaxial extensional flow. Melts are elongated to a Hencky strain of 6 at Rouse–Weissenberg numbers from 0.16 to 25, producing states with a wide range of chain alignment. Then flow is ceased and the systems are allowed to relax until twice the equilibrium disentanglement time. The relaxation of the stress is correlated with changes in the conformation of chains and the geometry of the tube confining them. Independent of initial alignment, chains relax to conformations consistent with the equilibrium tube length and diameter on the equilibrium Rouse time. Subsequent relaxation is the same for all systems and controlled by the equilibrium distentanglement time. These results are counter to prior work that indicates orientation causes a large, stretch-dependent reduction in the entanglement density that can only be recovered slowly by reptation on the equilibrium disentanglement time, raising fundamental questions about the nature of entanglement in aligned polymer melts.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Johns Hopkins Univ., Baltimore, MD (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1574479
Report Number(s):
SAND-2019-13792J
Journal ID: ISSN 0024-9297; 681376
Grant/Contract Number:  
AC04-94AL85000; NA-0003525
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 22; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

O’Connor, Thomas C., Hopkins, Austin, and Robbins, Mark O. Stress Relaxation in Highly Oriented Melts of Entangled Polymers. United States: N. p., 2019. Web. doi:10.1021/acs.macromol.9b01161.
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O’Connor, Thomas C., Hopkins, Austin, & Robbins, Mark O. Stress Relaxation in Highly Oriented Melts of Entangled Polymers. United States. https://doi.org/10.1021/acs.macromol.9b01161
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O’Connor, Thomas C., Hopkins, Austin, and Robbins, Mark O. Mon . "Stress Relaxation in Highly Oriented Melts of Entangled Polymers". United States. https://doi.org/10.1021/acs.macromol.9b01161. https://www.osti.gov/servlets/purl/1574479.
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@article{osti_1574479,
title = {Stress Relaxation in Highly Oriented Melts of Entangled Polymers},
author = {O’Connor, Thomas C. and Hopkins, Austin and Robbins, Mark O.},
abstractNote = {Here, molecular dynamics simulations are used to study relaxation of entangled polymer melts deformed far from equilibrium by uniaxial extensional flow. Melts are elongated to a Hencky strain of 6 at Rouse–Weissenberg numbers from 0.16 to 25, producing states with a wide range of chain alignment. Then flow is ceased and the systems are allowed to relax until twice the equilibrium disentanglement time. The relaxation of the stress is correlated with changes in the conformation of chains and the geometry of the tube confining them. Independent of initial alignment, chains relax to conformations consistent with the equilibrium tube length and diameter on the equilibrium Rouse time. Subsequent relaxation is the same for all systems and controlled by the equilibrium distentanglement time. These results are counter to prior work that indicates orientation causes a large, stretch-dependent reduction in the entanglement density that can only be recovered slowly by reptation on the equilibrium disentanglement time, raising fundamental questions about the nature of entanglement in aligned polymer melts.},
doi = {10.1021/acs.macromol.9b01161},
journal = {Macromolecules},
number = 22,
volume = 52,
place = {United States},
year = {2019},
month = {10}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.macromol.9b01161
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Cited by: 7 works
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Figures / Tables:

Table 1 Table 1: Tube Theory Parameters for the Bead-Spring Polymer Model with $k$bend = 1.5, $p$ = 0.85, and $T$ = 1$a$
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Works referenced in this record:

Quantitative Theory for Linear Dynamics of Linear Entangled Polymers
journal, July 2002

  • Likhtman, Alexei E.; McLeish, Tom C. B.
  • Macromolecules, Vol. 35, Issue 16
  • DOI: 10.1021/ma0200219

Analytic slip-link expressions for universal dynamic modulus predictions of linear monodisperse polymer melts
journal, January 2015

Elongational Viscosity of Narrow Molar Mass Distribution Polystyrene
journal, July 2003

  • Bach, Anders; Almdal, Kristoffer; Rasmussen, Henrik Koblitz
  • Macromolecules, Vol. 36, Issue 14
  • DOI: 10.1021/ma034279q

Elongational viscosity of monodisperse and bidisperse polystyrene melts
journal, July 2006

  • Nielsen, Jens Kromann; Rasmussen, Henrik Koblitz; Hassager, Ole
  • Journal of Rheology, Vol. 50, Issue 4
  • DOI: 10.1122/1.2206711

Stress relaxation of narrow molar mass distribution polystyrene following uniaxial extension
journal, July 2008

  • Nielsen, Jens Kromann; Rasmussen, Henrik Koblitz; Hassager, Ole
  • Journal of Rheology, Vol. 52, Issue 4
  • DOI: 10.1122/1.2930872

Extensional Rheology of Entangled Polystyrene Solutions Suggests Importance of Nematic Interactions
journal, July 2013

  • Huang, Qian; Alvarez, Nicolas J.; Matsumiya, Yumi
  • ACS Macro Letters, Vol. 2, Issue 8
  • DOI: 10.1021/mz400319v

Stress relaxation following uniaxial extension of polystyrene melt and oligomer dilutions
journal, May 2016

  • Huang, Qian; Rasmussen, Henrik Koblitz
  • Journal of Rheology, Vol. 60, Issue 3
  • DOI: 10.1122/1.4944995

Chain Retraction in Highly Entangled Stretched Polymer Melts
journal, October 2018

Effect of Finite Extensibility on Nonlinear Extensional Rheology of Polymer Melts
journal, January 2019

Relating Chain Conformations to Extensional Stress in Entangled Polymer Melts
journal, July 2018

Convective constraint release (CCR) revisited
journal, January 2014

  • Ianniruberto, Giovanni; Marrucci, Giuseppe
  • Journal of Rheology, Vol. 58, Issue 1
  • DOI: 10.1122/1.4843957

Quantitative appraisal of a new CCR model for entangled linear polymers
journal, January 2015

  • Ianniruberto, Giovanni
  • Journal of Rheology, Vol. 59, Issue 1
  • DOI: 10.1122/1.4903495

A constitutive model for entangled polymers incorporating binary entanglement pair dynamics and a configuration dependent friction coefficient
journal, March 2015

  • Mead, David W.; Banerjee, Nilanjana; Park, Joontaek
  • Journal of Rheology, Vol. 59, Issue 2
  • DOI: 10.1122/1.4905921

Rheology and Entanglement Structure of Well-Entangled Polymer Melts: A Slip-Link Simulation Study
journal, May 2019

Shear and Extensional Rheology of Polystyrene Melts and Solutions with the Same Number of Entanglements
journal, May 2016

Deformation of an amorphous polymer during the fused-filament-fabrication method for additive manufacturing
journal, March 2017

  • McIlroy, Claire; Olmsted, Peter D.
  • Journal of Rheology, Vol. 61, Issue 2
  • DOI: 10.1122/1.4976839

Fingerprinting Molecular Relaxation in Deformed Polymers
journal, July 2017

Molecular simulation of flow-enhanced nucleation in n -eicosane melts under steady shear and uniaxial extension
journal, December 2016

  • Nicholson, David A.; Rutledge, Gregory C.
  • The Journal of Chemical Physics, Vol. 145, Issue 24
  • DOI: 10.1063/1.4972894

An assessment of models for flow-enhanced nucleation in an n -alkane melt by molecular simulation
journal, May 2019

  • Nicholson, David A.; Rutledge, Gregory C.
  • Journal of Rheology, Vol. 63, Issue 3
  • DOI: 10.1122/1.5091945

Periodic boundary conditions for long-time nonequilibrium molecular dynamics simulations of incompressible flows
journal, November 2014

  • Dobson, Matthew
  • The Journal of Chemical Physics, Vol. 141, Issue 18
  • DOI: 10.1063/1.4901276

Rheology and Microscopic Topology of Entangled Polymeric Liquids
journal, February 2004

Shortest multiple disconnected path for the analysis of entanglements in two- and three-dimensional polymeric systems
journal, June 2005

Dynamics of entangled linear polymer melts:  A molecular‐dynamics simulation
journal, April 1990

  • Kremer, Kurt; Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 92, Issue 8
  • DOI: 10.1063/1.458541

Primitive Chain Network Simulation of Elongational Flows of Entangled Linear Chains: Stretch/Orientation-induced Reduction of Monomeric Friction
journal, March 2012

  • Yaoita, Takatoshi; Isaki, Takeharu; Masubuchi, Yuichi
  • Macromolecules, Vol. 45, Issue 6
  • DOI: 10.1021/ma202525v

Stretch/orientation Induced Acceleration in Stress Relaxation in Coarse-grained Molecular Dynamics Simulations
journal, January 2013

  • Masubuchi, Yuichi; Yaoita, Takatoshi; Matsumiya, Yumi
  • Nihon Reoroji Gakkaishi, Vol. 41, Issue 1
  • DOI: 10.1678/rheology.41.35

Communication: Polymer entanglement dynamics: Role of attractive interactions
journal, October 2016

  • Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 145, Issue 14
  • DOI: 10.1063/1.4964617

Direct Equilibration and Characterization of Polymer Melts for Computer Simulations: Direct Equilibration and Characterization of Polymer …
journal, June 2015

  • Moreira, Livia A.; Zhang, Guojie; Müller, Franziska
  • Macromolecular Theory and Simulations, Vol. 24, Issue 5
  • DOI: 10.1002/mats.201500013

Static and dynamic properties of large polymer melts in equilibrium
journal, April 2016

  • Hsu, Hsiao-Ping; Kremer, Kurt
  • The Journal of Chemical Physics, Vol. 144, Issue 15
  • DOI: 10.1063/1.4946033

Stress Relaxation in Entangled Polymer Melts
journal, August 2010

Double Reptation vs. Simple Reptation in Polymer Melts
journal, March 1988

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Nonlinear-response theory for steady planar Couette flow
journal, September 1984

A simple, direct derivation and proof of the validity of the SLLOD equations of motion for generalized homogeneous flows
journal, May 2006

  • Daivis, Peter J.; Todd, B. D.
  • The Journal of Chemical Physics, Vol. 124, Issue 19
  • DOI: 10.1063/1.2192775

Entanglements in Glassy Polymer Crazing: Cross-Links or Tubes?
journal, December 2016

Strain Hardening in Polymer Glasses: Limitations of Network Models
journal, September 2007

Concentrated Polymer Solutions are Different from Melts: Role of Entanglement Molecular Weight
journal, June 2013

  • Huang, Qian; Mednova, Olga; Rasmussen, Henrik K.
  • Macromolecules, Vol. 46, Issue 12
  • DOI: 10.1021/ma4008434

Bridging the Gap between Polymer Melts and Solutions in Extensional Rheology
journal, June 2015

Nonlinear Elongational Rheology of Unentangled Polystyrene and Poly( p - tert- butylstyrene) Melts
journal, November 2018

Rouse Mode Analysis of Chain Relaxation in Homopolymer Melts
journal, September 2014

  • Kalathi, Jagannathan T.; Kumar, Sanat K.; Rubinstein, Michael
  • Macromolecules, Vol. 47, Issue 19
  • DOI: 10.1021/ma500900b

The Shapes of Random Walks
journal, July 1987

Reptation of a Polymer Chain in the Presence of Fixed Obstacles
journal, July 1971

  • de Gennes, P. G.
  • The Journal of Chemical Physics, Vol. 55, Issue 2
  • DOI: 10.1063/1.1675789

Approximations of the discrete slip-link model and their effect on nonlinear rheology predictions
journal, March 2013

  • Andreev, Marat; Khaliullin, Renat N.; Steenbakkers, Rudi J. A.
  • Journal of Rheology, Vol. 57, Issue 2
  • DOI: 10.1122/1.4788909

Molecular Dynamics Investigation of the Relaxation Mechanism of Entangled Polymers after a Large Step Deformation
journal, January 2018

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    Topological Linking Drives Anomalous Thickening of Ring Polymers in Weak Extensional Flows
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