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Title: Rouse mode analysis of chain relaxation in polymer nanocomposites

Abstract

Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. In this paper, we examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, as in the case of a polymer–solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Furthermore, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Finally, our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.

Authors:
 [1];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; National Inst. of Technology Karnataka, Surathkal (India). Dept. of Chemical Engineering
  2. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  3. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Columbia Univ., New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); National Inst. of Health (NIH) (United States); Cystic Fibrosis Foundation (United States)
Contributing Org.:
Univ. of North Carolina, Chapel Hill, NC (United States); National Inst. of Technology Karnataka, Surathkal (India)
OSTI Identifier:
1235359
Alternate Identifier(s):
OSTI ID: 1340251
Report Number(s):
SAND-2015-2617J; SAND2014-19679J
Journal ID: ISSN 1744-683X; SMOABF; 581967
Grant/Contract Number:  
AC04-94AL85000; AC02-05CH11231; DMR-1006514; DMR-1309892; DMR-1436201; DMR-1121107; DMR-1122483; 1-P01-HL108808-01A1
Resource Type:
Accepted Manuscript
Journal Name:
Soft Matter
Additional Journal Information:
Journal Volume: 11; Journal Issue: 20; Journal ID: ISSN 1744-683X
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Kalathi, Jagannathan T., Kumar, Sanat K., Rubinstein, Michael, and Grest, Gary S. Rouse mode analysis of chain relaxation in polymer nanocomposites. United States: N. p., 2015. Web. doi:10.1039/c5sm00754b.
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Kalathi, Jagannathan T., Kumar, Sanat K., Rubinstein, Michael, & Grest, Gary S. Rouse mode analysis of chain relaxation in polymer nanocomposites. United States. https://doi.org/10.1039/c5sm00754b
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Kalathi, Jagannathan T., Kumar, Sanat K., Rubinstein, Michael, and Grest, Gary S. Mon . "Rouse mode analysis of chain relaxation in polymer nanocomposites". United States. https://doi.org/10.1039/c5sm00754b. https://www.osti.gov/servlets/purl/1235359.
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@article{osti_1235359,
title = {Rouse mode analysis of chain relaxation in polymer nanocomposites},
author = {Kalathi, Jagannathan T. and Kumar, Sanat K. and Rubinstein, Michael and Grest, Gary S.},
abstractNote = {Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. In this paper, we examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, as in the case of a polymer–solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Furthermore, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Finally, our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.},
doi = {10.1039/c5sm00754b},
journal = {Soft Matter},
number = 20,
volume = 11,
place = {United States},
year = {Mon Apr 20 00:00:00 EDT 2015},
month = {Mon Apr 20 00:00:00 EDT 2015}
}
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https://doi.org/10.1039/c5sm00754b
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Works referenced in this record:

Polymer Nanocomposites: The “Nano” Effect on Mechanical Properties
journal, April 2007

Equilibration of long chain polymer melts in computer simulations
journal, December 2003

  • Auhl, Rolf; Everaers, Ralf; Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1628670

Hybrid Nanorod-Polymer Solar Cells
journal, March 2002

  • Huynh, W. U.; Dittmer, Janke J.; Alivisatos, A. Paul
  • Science, Vol. 295, Issue 5564, p. 2425-2427
  • DOI: 10.1126/science.1069156

Universal scaling between structural relaxation and vibrational dynamics in glass-forming liquids and polymers
journal, December 2007

  • Larini, L.; Ottochian, A.; De Michele, C.
  • Nature Physics, Vol. 4, Issue 1
  • DOI: 10.1038/nphys788

Accurate and efficient methods for modeling colloidal mixtures in an explicit solvent using molecular dynamics
journal, September 2008

  • in 't Veld, Pieter J.; Plimpton, Steven J.; Grest, Gary S.
  • Computer Physics Communications, Vol. 179, Issue 5
  • DOI: 10.1016/j.cpc.2008.03.005

Simulating the miscibility of nanoparticles and polymer melts
journal, January 2013

  • Meng, Dong; Kumar, Sanat K.; Cheng, Shengfeng
  • Soft Matter, Vol. 9, Issue 22
  • DOI: 10.1039/c3sm50460c

A molecular dynamics simulation study of the viscoelastic properties of polymer nanocomposites
journal, November 2002

  • Smith, Grant D.; Bedrov, Dmitry; Li, Liwei
  • The Journal of Chemical Physics, Vol. 117, Issue 20
  • DOI: 10.1063/1.1516589

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

Structure and dynamics of carbon black-filled elastomers
journal, January 2000

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

Nanocomposites for food packaging applications
journal, November 2009

Nanoparticle Diffusion in Polymer Nanocomposites
journal, March 2014

Hopping Diffusion of Nanoparticles in Polymer Matrices
journal, January 2015

  • Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma501608x

Universal Viscosity Behavior of Polymer Nanocomposites
journal, November 2012

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

Chain Conformation in Polymer Nanocomposites with Uniformly Dispersed Nanoparticles
journal, May 2013

Identifying the primitive path mesh in entangled polymer liquids
journal, January 2005

  • Sukumaran, Sathish K.; Grest, Gary S.; Kremer, Kurt
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 8
  • DOI: 10.1002/polb.20384

Interaction potentials for soft and hard ellipsoids
journal, April 2003

Polymer-filler interactions in rubber reinforcement
journal, October 1990

Non-Gaussian effects in the cage dynamics of polymers
journal, November 2008

A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers
journal, July 1953

  • Rouse, Prince E.
  • The Journal of Chemical Physics, Vol. 21, Issue 7
  • DOI: 10.1063/1.1699180

Dynamics of Entangled Chains in Polymer Nanocomposites
journal, August 2011

  • Schneider, G. J.; Nusser, K.; Willner, L.
  • Macromolecules, Vol. 44, Issue 15
  • DOI: 10.1021/ma200899y

Effective potentials between nanoparticles in suspension
journal, April 2011

  • Grest, Gary S.; Wang, Qifei; Veld, Pieter in't
  • The Journal of Chemical Physics, Vol. 134, Issue 14
  • DOI: 10.1063/1.3578181

Time and length scales of polymer melts studied by coarse-grained molecular dynamics simulations
journal, July 2002

  • Padding, J. T.; Briels, W. J.
  • The Journal of Chemical Physics, Vol. 117, Issue 2
  • DOI: 10.1063/1.1481859

Controlling the Morphology of Nanocrystal–Polymer Composites for Solar Cells
journal, January 2003

  • Huynh, W. U.; Dittmer, J. J.; Libby, W. C.
  • Advanced Functional Materials, Vol. 13, Issue 1
  • DOI: 10.1002/adfm.200390009

Effects of chain topology on polymer dynamics: Configurational relaxation in polymer melts
journal, July 1995

  • Shaffer, J. Scott
  • The Journal of Chemical Physics, Vol. 103, Issue 2
  • DOI: 10.1063/1.470108

Anomalous chain diffusion in unentangled model polymer nanocomposites
journal, January 2013

  • Schneider, Gerald J.; Nusser, Klaus; Neueder, Susanne
  • Soft Matter, Vol. 9, Issue 16
  • DOI: 10.1039/c3sm27886g

Mobility of Nonsticky Nanoparticles in Polymer Liquids
journal, October 2011

  • Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael
  • Macromolecules, Vol. 44, Issue 19
  • DOI: 10.1021/ma201583q

Dynamics of polymer “isotope” mixtures: Molecular dynamics simulation and Rouse model analysis
journal, November 1997

  • Kopf, A.; Dünweg, B.; Paul, W.
  • The Journal of Chemical Physics, Vol. 107, Issue 17
  • DOI: 10.1063/1.474934

Dynamics of n-alkanes: Comparison to Rouse model
journal, July 1998

  • Mondello, Maurizio; Grest, Gary S.; Webb, Edmund B.
  • The Journal of Chemical Physics, Vol. 109, Issue 2
  • DOI: 10.1063/1.476619

Study of the dynamics of poly(ethylene oxide) by combining molecular dynamic simulations and neutron scattering experiments
journal, March 2009

  • Brodeck, M.; Alvarez, F.; Arbe, A.
  • The Journal of Chemical Physics, Vol. 130, Issue 9
  • DOI: 10.1063/1.3077858

Linear and Nonlinear Viscoelasticity of a Model Unentangled Polymer Melt: Molecular Dynamics and Rouse Modes Analysis
journal, April 2006

  • Vladkov, Mihail; Barrat, Jean-Louis
  • Macromolecular Theory and Simulations, Vol. 15, Issue 3
  • DOI: 10.1002/mats.200500079

The effect of Brownian motion on the bulk stress in a suspension of spherical particles
journal, November 1977

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

Liquid-vapor coexistence for nanoparticles of various size
journal, October 2008

  • in’ t. Veld, Pieter J.; Horsch, Mark A.; Lechman, Jeremy B.
  • The Journal of Chemical Physics, Vol. 129, Issue 16
  • DOI: 10.1063/1.2996513

Potential perspectives of bio-nanocomposites for food packaging applications
journal, February 2007

  • Sorrentino, Andrea; Gorrasi, Giuliana; Vittoria, Vittoria
  • Trends in Food Science & Technology, Vol. 18, Issue 2
  • DOI: 10.1016/j.tifs.2006.09.004

Microscopic origin of the terminal relaxation time in polymer nanocomposites: an experimental precedent
journal, January 2011

  • Nusser, Klaus; Schneider, Gerald J.; Richter, Dieter
  • Soft Matter, Vol. 7, Issue 18
  • DOI: 10.1039/c1sm05555k

Mobility of Nonsticky Nanoparticles in Polymer Liquids
text, January 2011

  • Sergey, Panyukov,; Michael, Rubinstein,; Li-Heng, Cai,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/9d2w-ss96

Rouse Mode Analysis of Chain Relaxation in Homopolymer Melts
text, January 2014

  • K., Kumar, Sanat; S., Grest, Gary; Michael, Rubinstein,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/m41d-9g92

Hopping Diffusion of Nanoparticles in Polymer Matrices
text, January 2015

  • Li-Heng, Cai,; Michael, Rubinstein,; Sergey, Panyukov,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/mn3f-j015

Interaction potentials for soft and hard ellipsoids
text, January 2003

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    journal, May 2017

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