skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites

Abstract

The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5]; ORCiD logo [6]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Physics and Astronomy
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical & Engineering Materials Division
  5. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  6. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Physics and Astronomy; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1410906
Alternate Identifier(s):
OSTI ID: 1409229
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; polymer nanocomposites; polymer dynamics; mechanical reinforcement; quasi-elastic neutron scattering; Brillouin scattering

Citation Formats

Holt, Adam P., Bocharova, Vera, Cheng, Shiwang, Kisliuk, Alexander M., Ehlers, Georg, Mamontov, Eugene, Novikov, Vladimir N., and Sokolov, Alexei P. Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites. United States: N. p., 2017. Web. doi:10.1103/PhysRevMaterials.1.062601.
Holt, Adam P., Bocharova, Vera, Cheng, Shiwang, Kisliuk, Alexander M., Ehlers, Georg, Mamontov, Eugene, Novikov, Vladimir N., & Sokolov, Alexei P. Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites. United States. doi:10.1103/PhysRevMaterials.1.062601.
Holt, Adam P., Bocharova, Vera, Cheng, Shiwang, Kisliuk, Alexander M., Ehlers, Georg, Mamontov, Eugene, Novikov, Vladimir N., and Sokolov, Alexei P. Fri . "Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites". United States. doi:10.1103/PhysRevMaterials.1.062601. https://www.osti.gov/servlets/purl/1410906.
@article{osti_1410906,
title = {Interplay between local dynamics and mechanical reinforcement in glassy polymer nanocomposites},
author = {Holt, Adam P. and Bocharova, Vera and Cheng, Shiwang and Kisliuk, Alexander M. and Ehlers, Georg and Mamontov, Eugene and Novikov, Vladimir N. and Sokolov, Alexei P.},
abstractNote = {The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.},
doi = {10.1103/PhysRevMaterials.1.062601},
journal = {Physical Review Materials},
number = 6,
volume = 1,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites
journal, March 2007

  • Rittigstein, Perla; Priestley, Rodney D.; Broadbelt, Linda J.
  • Nature Materials, Vol. 6, Issue 4
  • DOI: 10.1038/nmat1870

Polymer–nanoparticle interfacial interactions in polymer nanocomposites: Confinement effects on glass transition temperature and suppression of physical aging
journal, January 2006

  • Rittigstein, Perla; Torkelson, John M.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 20
  • DOI: 10.1002/polb.20925

Experimental trends in polymer nanocomposites—a review
journal, February 2005

  • Jordan, Jeffrey; Jacob, Karl I.; Tannenbaum, Rina
  • Materials Science and Engineering: A, Vol. 393, Issue 1-2
  • DOI: 10.1016/j.msea.2004.09.044

Detection of Surface-Immobilized Components and Their Role in Viscoelastic Reinforcement of Rubber–Silica Nanocomposites
journal, April 2014

  • Mujtaba, A.; Keller, M.; Ilisch, S.
  • ACS Macro Letters, Vol. 3, Issue 5
  • DOI: 10.1021/mz500192r

Mechanical Properties of Thin Glassy Polymer Films Filled with Spherical Polymer-Grafted Nanoparticles
journal, July 2012

  • Maillard, Damien; Kumar, Sanat K.; Fragneaud, Benjamin
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301792g

Origin of Glass Transition of Poly(2-vinylpyridine). A Temperature- and Pressure-Dependent Dielectric Spectroscopy Study
journal, October 2004

  • Papadopoulos, P.; Peristeraki, D.; Floudas, G.
  • Macromolecules, Vol. 37, Issue 21
  • DOI: 10.1021/ma048555s

Model interfaces
journal, April 2007


Effect of binding to carbon black on the dynamics of 1,4-polybutadiene
journal, October 2013

  • Roh, J. H.; Tyagi, M.; Hogan, T. E.
  • The Journal of Chemical Physics, Vol. 139, Issue 13
  • DOI: 10.1063/1.4822476

Local and Global Dynamics in Polypropylene Glycol/Silica Composites
journal, May 2016


Focus: Structure and dynamics of the interfacial layer in polymer nanocomposites with attractive interactions
journal, May 2017

  • Cheng, Shiwang; Carroll, Bobby; Bocharova, Vera
  • The Journal of Chemical Physics, Vol. 146, Issue 20
  • DOI: 10.1063/1.4978504

A new Brillouin scattering technique for the investigation of acoustic and opto-acoustic properties: application to polymers
journal, August 1998

  • Krüger, Jan K.; Embs, Jan; Brierley, Justin
  • Journal of Physics D: Applied Physics, Vol. 31, Issue 15
  • DOI: 10.1088/0022-3727/31/15/021

Modifying Fragility and Collective Motion in Polymer Melts with Nanoparticles
journal, March 2011


On the mechanical γ-relaxation modes of polycarbonate
journal, January 1992


Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids
journal, June 2016


Effect of molecular weight and temperature on physical aging of thin glassy poly(2,6-dimethyl-1,4-phenylene oxide) films
journal, January 2007

  • Huang, Y.; Paul, D. R.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 12
  • DOI: 10.1002/polb.21173

Relaxation Phenomena in Vitrifying Polymers and Molecular Liquids
journal, October 2010


Nanoscale visualization and multiscale mechanical implications of bound rubber interphases in rubber–carbon black nanocomposites
journal, January 2011

  • Qu, Meng; Deng, Fei; Kalkhoran, Salmon M.
  • Soft Matter, Vol. 7, Issue 3
  • DOI: 10.1039/C0SM00645A

Relaxation Dynamics of Nanoparticle-Tethered Polymer Chains
journal, August 2015


Short time and Structural Dynamics in Polypropylene Glycol Nanocomposite
journal, June 2017

  • Tyagi, M.; Casalini, R.; Roland, C. M.
  • Rubber Chemistry and Technology, Vol. 90, Issue 2
  • DOI: 10.5254/rct.17.82664

Theory of glassy dynamics in conformationally anisotropic polymer systems
journal, December 2005

  • Oyerokun, Folusho T.; Schweizer, Kenneth S.
  • The Journal of Chemical Physics, Vol. 123, Issue 22
  • DOI: 10.1063/1.2135776

Anisotropic Elasticity of Quasi-One-Component Polymer Nanocomposites
journal, June 2011

  • Voudouris, Panayiotis; Choi, Jihoon; Gomopoulos, Nikos
  • ACS Nano, Vol. 5, Issue 7
  • DOI: 10.1021/nn201431w

Antiplasticization effects on a secondary relaxation in plasticized glassy polycarbonates
journal, January 1991

  • Ngai, K. L.; Rendell, R. W.; Yee, A. F.
  • Macromolecules, Vol. 24, Issue 1
  • DOI: 10.1021/ma00001a010

Probing Soft Matter with the Atomic Force Microscopies: Imaging and Force Spectroscopy
journal, July 2010


Molecular Dynamics Simulation of a Polymer Melt with a Nanoscopic Particle
journal, May 2002

  • Starr, Francis W.; Schrøder, Thomas B.; Glotzer, Sharon C.
  • Macromolecules, Vol. 35, Issue 11
  • DOI: 10.1021/ma010626p

Fragility and cooperative motion in a glass-forming polymer–nanoparticle composite
journal, January 2013

  • Pazmiño Betancourt, Beatriz A.; Douglas, Jack F.; Starr, Francis W.
  • Soft Matter, Vol. 9, Issue 1
  • DOI: 10.1039/C2SM26800K

Dielectric Spectroscopy Investigation of Relaxation in C 60 −Polyisoprene Nanocomposites
journal, April 2009

  • Ding, Yifu; Pawlus, Sebastian; Sokolov, Alexei P.
  • Macromolecules, Vol. 42, Issue 8
  • DOI: 10.1021/ma8024333

Unexpected Molecular Weight Effect in Polymer Nanocomposites
journal, January 2016


Quantitative equivalence between polymer nanocomposites and thin polymer films
journal, August 2005

  • Bansal, Amitabh; Yang, Hoichang; Li, Chunzhao
  • Nature Materials, Vol. 4, Issue 9
  • DOI: 10.1038/nmat1447

The influence of blending on the local motions of polymers. Studies involving polycarbonate, poly(methyl methacrylate), and a polyester
journal, September 1989

  • Landry, Christine J. T.; Henrichs, P. Mark
  • Macromolecules, Vol. 22, Issue 5
  • DOI: 10.1021/ma00195a027

Mechanics of the rate-dependent elastic–plastic deformation of glassy polymers from low to high strain rates
journal, March 2006


Local Polymer Dynamics in Polymer−C 60 Mixtures
journal, April 2008

  • Kropka, Jamie M.; Garcia Sakai, Victoria; Green, Peter F.
  • Nano Letters, Vol. 8, Issue 4
  • DOI: 10.1021/nl072980s

Local molecular motions in glassy and dissolved polycarbonates
journal, December 1988

  • Ngai, K. L.; Rendell, R. W.; Yee, A. F.
  • Macromolecules, Vol. 21, Issue 12
  • DOI: 10.1021/ma00190a009

Correlation between the Shear Yielding Behavior and Secondary Relaxations of Bisphenol A Polycarbonate and Related Copolymers
journal, May 1994

  • Xiao, Chaodong; Jho, Jae Young; Yee, Albert F.
  • Macromolecules, Vol. 27, Issue 10
  • DOI: 10.1021/ma00088a017

Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites
journal, June 2016


Dynamics near the filler surface in natural rubber-silica nanocomposites
journal, June 2011


Size-Dependent Permeability Deviations from Maxwell’s Model in Hybrid Cross-Linked Poly(ethylene glycol)/Silica Nanoparticle Membranes
journal, March 2015

  • Su, Norman C.; Smith, Zachary P.; Freeman, Benny D.
  • Chemistry of Materials, Vol. 27, Issue 7
  • DOI: 10.1021/cm504463c

Bound Polymer Layer in Nanocomposites
journal, April 2013

  • Jouault, Nicolas; Moll, Joseph F.; Meng, Dong
  • ACS Macro Letters, Vol. 2, Issue 5
  • DOI: 10.1021/mz300646a

Modified chain dynamics in poly(dimethylsiloxane)/silica nanocomposites
journal, November 2006


Unraveling the Mechanism of Nanoscale Mechanical Reinforcement in Glassy Polymer Nanocomposites
journal, May 2016


Controlling the Thermomechanical Behavior of Nanoparticle/Polymer Films
journal, July 2014

  • Zhao, Dan; Schneider, Dirk; Fytas, George
  • ACS Nano, Vol. 8, Issue 8
  • DOI: 10.1021/nn503486e

The cold neutron chopper spectrometer at the Spallation Neutron Source—A review of the first 8 years of operation
journal, September 2016

  • Ehlers, G.; Podlesnyak, A. A.; Kolesnikov, A. I.
  • Review of Scientific Instruments, Vol. 87, Issue 9
  • DOI: 10.1063/1.4962024

A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS
journal, August 2011

  • Mamontov, E.; Herwig, K. W.
  • Review of Scientific Instruments, Vol. 82, Issue 8
  • DOI: 10.1063/1.3626214

Glass Transitions in Highly Attractive Highly Filled Polymer Nanocomposites
journal, January 2012

  • Moll, Joseph; Kumar, Sanat K.
  • Macromolecules, Vol. 45, Issue 2
  • DOI: 10.1021/ma202218x

Space-Dependent Dynamics in 1,4-Polybutadiene Nanocomposite
journal, August 2013

  • Roh, J. H.; Tyagi, M.; Hogan, T. E.
  • Macromolecules, Vol. 46, Issue 16
  • DOI: 10.1021/ma401597r