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Title: Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites

Abstract

It is generally believed that the strength of the polymer nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface ismore » affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching a parameter accessible from the MW or grafting density.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [2];  [3];  [4];  [4];  [5];  [5];  [5];  [6];  [4];  [7];  [7]
  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). Center for Nanophase Materials Sciences (CNMS)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computer Science and Mathematics Division
  5. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  6. Columbus State Univ., Columbus, GA (United States). Dept. of Chemistry
  7. 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). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1302936
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 10; Journal Issue: 7; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; glass transition; interfacial dynamics; polymer nanocomposites; polymer-grafted nanoparticles; segmental dynamics; self-consistent field theory

Citation Formats

Holt, Adam P., Bocharova, Vera, Cheng, Shiwang, Kisliuk, Alexander M., White, B. Tyler, Saito, Tomonori, Uhrig, David, Mahalik, J. P., Kumar, Rajeev, Imel, Adam E., Etampawala, Thusitha, Martin, Halie, Sikes, Nicole, Sumpter, Bobby G., Dadmun, Mark D., and Sokolov, Alexei P. Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites. United States: N. p., 2016. Web. doi:10.1021/acsnano.6b02501.
Holt, Adam P., Bocharova, Vera, Cheng, Shiwang, Kisliuk, Alexander M., White, B. Tyler, Saito, Tomonori, Uhrig, David, Mahalik, J. P., Kumar, Rajeev, Imel, Adam E., Etampawala, Thusitha, Martin, Halie, Sikes, Nicole, Sumpter, Bobby G., Dadmun, Mark D., & Sokolov, Alexei P. Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites. United States. https://doi.org/10.1021/acsnano.6b02501
Holt, Adam P., Bocharova, Vera, Cheng, Shiwang, Kisliuk, Alexander M., White, B. Tyler, Saito, Tomonori, Uhrig, David, Mahalik, J. P., Kumar, Rajeev, Imel, Adam E., Etampawala, Thusitha, Martin, Halie, Sikes, Nicole, Sumpter, Bobby G., Dadmun, Mark D., and Sokolov, Alexei P. Thu . "Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites". United States. https://doi.org/10.1021/acsnano.6b02501. https://www.osti.gov/servlets/purl/1302936.
@article{osti_1302936,
title = {Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites},
author = {Holt, Adam P. and Bocharova, Vera and Cheng, Shiwang and Kisliuk, Alexander M. and White, B. Tyler and Saito, Tomonori and Uhrig, David and Mahalik, J. P. and Kumar, Rajeev and Imel, Adam E. and Etampawala, Thusitha and Martin, Halie and Sikes, Nicole and Sumpter, Bobby G. and Dadmun, Mark D. and Sokolov, Alexei P.},
abstractNote = {It is generally believed that the strength of the polymer nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching a parameter accessible from the MW or grafting density.},
doi = {10.1021/acsnano.6b02501},
journal = {ACS Nano},
number = 7,
volume = 10,
place = {United States},
year = {2016},
month = {6}
}

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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

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


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

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

The amount of immobilized polymer in PMMA SiO2 nanocomposites determined from calorimetric data
journal, August 2007


Influence of Surface Grafted Polymers on the Polymer Dynamics in a Silica–Polystyrene Nanocomposite: A Coarse-Grained Molecular Dynamics Investigation
journal, November 2013

  • Ghanbari, Azadeh; Rahimi, Mohammad; Dehghany, Jaber
  • The Journal of Physical Chemistry C, Vol. 117, Issue 47
  • DOI: 10.1021/jp407109r

Interphase Structure in Silica–Polystyrene Nanocomposites: A Coarse-Grained Molecular Dynamics Study
journal, December 2011

  • Ghanbari, Azadeh; Ndoro, Tinashe V. M.; Leroy, Frédéric
  • Macromolecules, Vol. 45, Issue 1
  • DOI: 10.1021/ma202044e

Effect of nanoscale confinement on glass transition of polystyrene domains from self-assembly of block copolymers
journal, March 2010

  • Robertson, C. G.; Hogan, T. E.; Rackaitis, M.
  • The Journal of Chemical Physics, Vol. 132, Issue 10
  • DOI: 10.1063/1.3337910

When Does a Glass Transition Temperature Not Signify a Glass Transition?
journal, March 2014

  • Forrest, J. A.; Dalnoki-Veress, K.
  • ACS Macro Letters, Vol. 3, Issue 4
  • DOI: 10.1021/mz4006217

Interfacial mobility scale determines the scale of collective motion and relaxation rate in polymer films
journal, June 2014

  • Hanakata, Paul Z.; Douglas, Jack F.; Starr, Francis W.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5163

Glass Formation near Covalently Grafted Interfaces: Ionomers as a Model Case
journal, March 2015


Reversible crystallization and the rigid–amorphous phase in semicrystalline macromolecules
journal, March 2003


An Emerging Unified View of Dynamic Interphases in Polymers
journal, December 2015


Glass transition and molecular dynamics in poly(dimethylsiloxane)/silica nanocomposites
journal, July 2005


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


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

Unexpected Molecular Weight Effect in Polymer Nanocomposites
journal, January 2016


Dynamics at the Polymer/Nanoparticle Interface in Poly(2-vinylpyridine)/Silica Nanocomposites
journal, February 2014

  • Holt, Adam P.; Griffin, Philip J.; Bocharova, Vera
  • Macromolecules, Vol. 47, Issue 5
  • DOI: 10.1021/ma5000317

Immobilized Polymer Layers on Spherical Nanoparticles
journal, April 2010

  • Harton, Shane E.; Kumar, Sanat K.; Yang, Hoichang
  • Macromolecules, Vol. 43, Issue 7
  • DOI: 10.1021/ma902484d

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

Glass Transition and Interfacial Segmental Dynamics in Polymer-Particle Composites
journal, July 2008

  • Robertson, C. G.; Roland, C. M.
  • Rubber Chemistry and Technology, Vol. 81, Issue 3
  • DOI: 10.5254/1.3548217

Fragility is a Key Parameter in Determining the Magnitude of T g -Confinement Effects in Polymer Films
journal, July 2013

  • Evans, Christopher M.; Deng, Hui; Jager, Wolter F.
  • Macromolecules, Vol. 46, Issue 15
  • DOI: 10.1021/ma401017n

Combined FTIR and Dielectric Investigation of Poly(vinyl acetate) Adsorbed on Silica Particles
journal, May 2013

  • Füllbrandt, Marieke; Purohit, Purv J.; Schönhals, Andreas
  • Macromolecules, Vol. 46, Issue 11
  • DOI: 10.1021/ma400461p

Glass transition of poly(ethylmethacrylate) admixed and bound to nanoparticles
journal, March 2013

  • Friedrichs, Cornelius; Emmerling, Sebastian; Kircher, Gunnar
  • The Journal of Chemical Physics, Vol. 138, Issue 12
  • DOI: 10.1063/1.4769252

Crowded, Confined, and Frustrated: Dynamics of Molecules Tethered to Nanoparticles
journal, December 2012


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


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

Current issues in research on structure–property relationships in polymer nanocomposites
journal, July 2010


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

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


A neutron scattering study of the structure of a bimodal colloidal crystal
journal, February 1992

  • Bartlett, P.; Ottewill, R. H.
  • The Journal of Chemical Physics, Vol. 96, Issue 4
  • DOI: 10.1063/1.461926

Interface of Grafted and Ungrafted Silica Nanoparticles with a Polystyrene Matrix: Atomistic Molecular Dynamics Simulations
journal, April 2011

  • Ndoro, Tinashe V. M.; Voyiatzis, Evangelos; Ghanbari, Azadeh
  • Macromolecules, Vol. 44, Issue 7
  • DOI: 10.1021/ma102833u

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

High Ion Conducting Polymer Nanocomposite Electrolytes Using Hybrid Nanofillers
journal, February 2012

  • Tang, Changyu; Hackenberg, Ken; Fu, Qiang
  • Nano Letters, Vol. 12, Issue 3
  • DOI: 10.1021/nl202692y

Polymer–Graphene Nanocomposites as Ultrafast-Charge and -Discharge Cathodes for Rechargeable Lithium Batteries
journal, April 2012

  • Song, Zhiping; Xu, Terrence; Gordin, Mikhail L.
  • Nano Letters, Vol. 12, Issue 5
  • DOI: 10.1021/nl2039666

Revealing spatially heterogeneous relaxation in a model nanocomposite
journal, November 2015

  • Cheng, Shiwang; Mirigian, Stephen; Carrillo, Jan-Michael Y.
  • The Journal of Chemical Physics, Vol. 143, Issue 19
  • DOI: 10.1063/1.4935595

Dynamics of solvent-free grafted nanoparticles
journal, January 2012

  • Chremos, Alexandros; Panagiotopoulos, Athanassios Z.; Koch, Donald L.
  • The Journal of Chemical Physics, Vol. 136, Issue 4
  • DOI: 10.1063/1.3679442

Conformational Transitions of Spherical Polymer Brushes: Synthesis, Characterization, and Theory
journal, February 2010

  • Dukes, Douglas; Li, Yu; Lewis, Sarah
  • Macromolecules, Vol. 43, Issue 3
  • DOI: 10.1021/ma901228t

Scaling theory of polymer adsorption
journal, January 1976


Conformations of Polymers Attached to an Interface
journal, September 1980


Structure of densely grafted polymeric monolayers
journal, January 1988


Theory of the grafted polymer brush
journal, August 1988

  • Milner, S. T.; Witten, T. A.; Cates, M. E.
  • Macromolecules, Vol. 21, Issue 8
  • DOI: 10.1021/ma00186a051

Charge regulation and local dielectric function in planar polyelectrolyte brushes
journal, June 2012

  • Kumar, Rajeev; Sumpter, Bobby G.; Kilbey, S. Michael
  • The Journal of Chemical Physics, Vol. 136, Issue 23
  • DOI: 10.1063/1.4729158

Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes
journal, March 2016

  • Mahalik, J. P.; Yang, Yubo; Deodhar, Chaitra
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 10
  • DOI: 10.1002/polb.24008

Star shaped polymers : a model for the conformation and its concentration dependence
journal, January 1982


Microphase separation in thin films of lamellar forming polydisperse di-block copolymers
journal, January 2015

  • Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.
  • RSC Advances, Vol. 5, Issue 27
  • DOI: 10.1039/C5RA00974J

Segmental Dynamics of Polymer Melts with Spherical Nanoparticles
journal, July 2014

  • Gong, Shushan; Chen, Quan; Moll, Joseph F.
  • ACS Macro Letters, Vol. 3, Issue 8
  • DOI: 10.1021/mz500252f

Untangling the Effects of Chain Rigidity on the Structure and Dynamics of Strongly Adsorbed Polymer Melts
journal, June 2015


Layer-by-Layer Surface Modification of Functional Nanoparticles for Dispersion in Organic Solvents
journal, December 2010

  • Iijima, Motoyuki; Kamiya, Hidehiro
  • Langmuir, Vol. 26, Issue 23
  • DOI: 10.1021/la1030747

Densification of Alkoxide-Derived Fine Silica Powder Compact by Ultra-High-Pressure Cold Isostatic Pressing
journal, January 1993


Works referencing / citing this record:

Natural rubber–SiO 2 nanohybrids: interface structures and dynamics
journal, January 2019

  • Sattar, Md. Abdul; Nair, A. Sreekumaran; Xavier, P. J.
  • Soft Matter, Vol. 15, Issue 13
  • DOI: 10.1039/c9sm00254e

Direct observation of polymer surface mobility via nanoparticle vibrations
journal, July 2018


Initial Solvent-Driven Nonequilibrium Effect on Structure, Properties, and Dynamics of Polymer Nanocomposites
journal, October 2019


Recent Studies on the Multiscale Analysis of Polymer Nanocomposites
journal, July 2019


Polymer matrix nanocomposites for automotive structural components
journal, December 2016

  • Naskar, Amit K.; Keum, Jong K.; Boeman, Raymond G.
  • Nature Nanotechnology, Vol. 11, Issue 12
  • DOI: 10.1038/nnano.2016.262

Impact of uniaxial tensile fatigue on the evolution of microscopic and mesoscopic structure of carbon black filled natural rubber
journal, February 2019

  • Sun, Chong; Du, Zhongjin; Nagarajan, Selvaraj
  • Royal Society Open Science, Vol. 6, Issue 2
  • DOI: 10.1098/rsos.181883

Nanoparticle–polymer interfacial layer properties tune fragility and dynamic heterogeneity of athermal polymer nanocomposite films
journal, January 2018

  • Begam, Nafisa; Das A., Nimmi; Chandran, Sivasurender
  • Soft Matter, Vol. 14, Issue 43
  • DOI: 10.1039/c8sm01729h

Unexpected Molecular Weight Dependence to the Physical Aging of Thin Polystyrene Films Present at Ultra‐High Molecular Weights
journal, February 2019

  • Thees, Michael F.; Roth, Connie B.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 18
  • DOI: 10.1002/polb.24797

Dynamics of entangled polymer chains with nanoparticle attachment under large amplitude oscillatory shear
journal, November 2018

  • Hershey, Christopher; Jayaraman, Krishnamurthy
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 1
  • DOI: 10.1002/polb.24768

Polymer-particulate composites with differential interfaces: synthesis, characterization, and mathematical modeling to evaluate interface-yield strength correlations
journal, February 2019

  • Afzal, Adeel; Siddiqi, Humaira M.; Sarwar, Shahzad
  • Colloid and Polymer Science, Vol. 297, Issue 4
  • DOI: 10.1007/s00396-019-04477-7

Segmental and secondary dynamics of nanoparticle-grafted oligomers
journal, January 2018


Interfacial effects on crystallization behavior of polymer nanocomposites with polymer‐grafted nanoparticles
journal, June 2019

  • Wen, Xiangning; Zhao, Weiwei; Su, Yunlan
  • POLYMER CRYSTALLIZATION, Vol. 2, Issue 3
  • DOI: 10.1002/pcr2.10066

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

Grafting density dominant glass transition of dry polystyrene brushes
journal, January 2017

  • Zuo, Biao; Zhang, Shasha; Niu, Chen
  • Soft Matter, Vol. 13, Issue 13
  • DOI: 10.1039/c6sm02790c

Polymers on nanoparticles: structure & dynamics
journal, January 2019


Cu nanoparticles constrain segmental dynamics of cross-linked polyethers: a trade-off between non-fouling and antibacterial properties
journal, January 2019

  • Nikitin, Daniil; Madkour, Sherif; Pleskunov, Pavel
  • Soft Matter, Vol. 15, Issue 13
  • DOI: 10.1039/c8sm02413h

Fabrication and photocatalytic activity of LaFeO 3 ribbon‐like nanofibers
journal, December 2019

  • Li, Shudan; Guo, Meiling; Wang, Xiuhua
  • Journal of the Chinese Chemical Society, Vol. 67, Issue 6
  • DOI: 10.1002/jccs.201900431

Nanoparticle–polymer interfacial layer properties tune fragility and dynamic heterogeneity of athermal polymer nanocomposite films
text, January 2018

  • Begam, Nafisa; Das A., Nimmi; Chandran, Sivasurender
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2018-05897