Unexpected molecular weight effect in polymer nanocomposites

Cheng, Shiwang; Holt, Adam P.; Wang, Huiqun; Fan, Fei; Bocharova, Vera; Martin, Halie J.; Etampawala, Thusitha N.; White, Benjamin Tyler; Saito, Tomonori; Kang, Nam -Goo; Dadmun, Mark D.; Mays, Jimmy W.; Sokolov, Alexei P.

doi:10.1103/PhysRevLett.116.038302

Title: Unexpected molecular weight effect in polymer nanocomposites

Abstract

Here, the properties of the interfacial layer between the polymer matrix and nanoparticles largely determine the macroscopic properties of polymer nanocomposites (PNCs). Although the static thickness of the interfacial layer was found to increase with the molecular weight (MW), the influence of MW on segmental relaxation and the glass transition in this layer remains to be explored. In this Letter, we show an unexpected MW dependence of the interfacial properties in PNC with attractive polymer-nanoparticle interactions: the thickness of the interfacial layer with hindered segmental relaxation decreases as MW increases, in sharp constrast to theoretical predictions. Further analyses reveal a reduction in mass density of the interfacial layer with increasing MW, which can explain these unexpected dynamic effects. Our observations call for a significant revision of the current understandings of PNCs and suggest interesting ways to tailor their properties.

Authors:

Cheng, Shiwang ^[1]; Holt, Adam P. ^[2]; Wang, Huiqun ^[2]; Fan, Fei ^[2]; Bocharova, Vera ^[1]; Martin, Halie J. ^[2]; Etampawala, Thusitha N. ^[2]; White, Benjamin Tyler ^[1]; Saito, Tomonori ^[1]; Kang, Nam -Goo ^[2]; Dadmun, Mark D. ^[2]; Mays, Jimmy W. ^[2]; Sokolov, Alexei P. ^[3]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Publication Date:: Fri Jan 22 00:00:00 EST 2016

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1265983

Alternate Identifier(s):: OSTI ID: 1235749

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Physical Review Letters

Additional Journal Information:: Journal Volume: 116; Journal Issue: 3; Journal ID: ISSN 0031-9007

Publisher:: American Physical Society (APS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Cheng, Shiwang, Holt, Adam P., Wang, Huiqun, Fan, Fei, Bocharova, Vera, Martin, Halie J., Etampawala, Thusitha N., White, Benjamin Tyler, Saito, Tomonori, Kang, Nam -Goo, Dadmun, Mark D., Mays, Jimmy W., and Sokolov, Alexei P. Unexpected molecular weight effect in polymer nanocomposites.  United States: N. p., 2016. 
Web.  doi:10.1103/PhysRevLett.116.038302.

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                    Cheng, Shiwang, Holt, Adam P., Wang, Huiqun, Fan, Fei, Bocharova, Vera, Martin, Halie J., Etampawala, Thusitha N., White, Benjamin Tyler, Saito, Tomonori, Kang, Nam -Goo, Dadmun, Mark D., Mays, Jimmy W., & Sokolov, Alexei P. Unexpected molecular weight effect in polymer nanocomposites.  United States.  https://doi.org/10.1103/PhysRevLett.116.038302

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                    Cheng, Shiwang, Holt, Adam P., Wang, Huiqun, Fan, Fei, Bocharova, Vera, Martin, Halie J., Etampawala, Thusitha N., White, Benjamin Tyler, Saito, Tomonori, Kang, Nam -Goo, Dadmun, Mark D., Mays, Jimmy W., and Sokolov, Alexei P. Fri .  
"Unexpected molecular weight effect in polymer nanocomposites".  United States.  https://doi.org/10.1103/PhysRevLett.116.038302.  https://www.osti.gov/servlets/purl/1265983.

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@article{osti_1265983,

  title        = {Unexpected molecular weight effect in polymer nanocomposites},

  author       = {Cheng, Shiwang and Holt, Adam P. and Wang, Huiqun and Fan, Fei and Bocharova, Vera and Martin, Halie J. and Etampawala, Thusitha N. and White, Benjamin Tyler and Saito, Tomonori and Kang, Nam -Goo and Dadmun, Mark D. and Mays, Jimmy W. and Sokolov, Alexei P.},

  abstractNote = {Here, the properties of the interfacial layer between the polymer matrix and nanoparticles largely determine the macroscopic properties of polymer nanocomposites (PNCs). Although the static thickness of the interfacial layer was found to increase with the molecular weight (MW), the influence of MW on segmental relaxation and the glass transition in this layer remains to be explored. In this Letter, we show an unexpected MW dependence of the interfacial properties in PNC with attractive polymer-nanoparticle interactions: the thickness of the interfacial layer with hindered segmental relaxation decreases as MW increases, in sharp constrast to theoretical predictions. Further analyses reveal a reduction in mass density of the interfacial layer with increasing MW, which can explain these unexpected dynamic effects. Our observations call for a significant revision of the current understandings of PNCs and suggest interesting ways to tailor their properties.},

  doi          = {10.1103/PhysRevLett.116.038302},

  journal      = {Physical Review Letters},

  number       = 3,

  volume       = 116,

  place        = {United States},

  year         = {Fri Jan 22 00:00:00 EST 2016},

  month        = {Fri Jan 22 00:00:00 EST 2016}

}

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Title: Unexpected molecular weight effect in polymer nanocomposites

Abstract

Citation Formats

Polymer/layered silicate nanocomposites: a review from preparation to processing journal, November 2003

Applications of hybrid organic–inorganic nanocomposites journal, January 2005

Designed Interfaces in Polymer Nanocomposites: A Fundamental Viewpoint journal, April 2007

Nanocomposites: Structure, Phase Behavior, and Properties journal, June 2010

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

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Irreversible Adsorption of a Concentrated Polymer Solution journal, January 1992

Adsorption of Polymer Solutions onto a Flat Surface journal, January 1996

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Bound Polymer Layer in Nanocomposites journal, April 2013

The distribution of glass-transition temperatures in nanoscopically confined glass formers journal, September 2003

Effect of Silica Nanoparticles on the Local Segmental Dynamics in Poly(vinyl acetate) journal, February 2008

Immobilized Polymer Layers on Spherical Nanoparticles journal, April 2010

Probing interfacial mobility profiles via the impact of nanoscopic confinement on the strength of the dynamic glass transition journal, January 2011

Polymer Dynamics in PEG-Silica Nanocomposites: Effects of Polymer Molecular Weight, Temperature and Solvent Dilution journal, May 2012

Solid particles in an elastomer matrix: impact of colloid dispersion and polymer mobility modification on the mechanical properties journal, January 2012

Revealed Architectures of Adsorbed Polymer Chains at Solid-Polymer Melt Interfaces journal, December 2012

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

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

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Evidence for the Shift of the Glass Transition near the Particles in Silica-Filled Elastomers journal, December 2002

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

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

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

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

Impact of an Irreversibly Adsorbed Layer on Local Viscosity of Nanoconfined Polymer Melts journal, November 2011

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

Interfacial phenomena in core–shell nanocomposites of PDMS adsorbed onto low specific surface area fumed silica nanooxides: Effects of surface modification journal, June 2015

Interfacial dynamics of polydimethylsiloxane adsorbed on fumed metal oxide particles of a wide range of specific surface area journal, October 2015

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

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

An interlayer model for the complex dielectric constant of composites journal, April 1990

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Macromolecular Diffusion in a Crowded Polymer Nanocomposite journal, May 2011

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The lifetime of the deviations from bulk behaviour in polymers confined at the nanoscale journal, March 2011

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Opportunities in theoretical and computational polymeric materials and soft matter journal, January 2015

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Conformational changes underlying variation in the structural dynamics of materials confined at the nanometric scale journal, January 2018

Influence of molecular weight on molecular dynamics and dynamic rheology of polypropylene glycol filled with silica journal, January 2018

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

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

Influence of knot complexity on glass-formation in low molecular mass ring polymer melts journal, March 2019

Heterogeneous dynamics of unentangled chains in polymer nanocomposites journal, May 2019

The interfacial zone in thin polymer films and around nanoparticles in polymer nanocomposites journal, September 2019

Glass transition of polymers in bulk, confined geometries, and near interfaces journal, January 2017

Effect of Local Chain Conformation in Adsorbed Nanolayers on Confined Polymer Molecular Mobility journal, May 2019

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

Interfacial Properties and Hopping Diffusion of Small Nanoparticle in Polymer/Nanoparticle Composite with Attractive Interaction on Side Group journal, May 2018

Polymer/layered silicate nanocomposites: a review from preparation to processing
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Applications of hybrid organic–inorganic nanocomposites
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Designed Interfaces in Polymer Nanocomposites: A Fundamental Viewpoint
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Nanocomposites: Structure, Phase Behavior, and Properties
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Current issues in research on structure–property relationships in polymer nanocomposites
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Nanoscale effects leading to non-Einstein-like decrease in viscosity
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Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites
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Statistical theory of the adsorption of interacting chain molecules. 2. Train, loop, and tail size distribution
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Polymers at an interface; a simplified view
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Irreversible Adsorption of a Concentrated Polymer Solution
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Adsorption of Polymer Solutions onto a Flat Surface
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Lattice models for bulk polymers at interfaces
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Bound Polymer Layer in Nanocomposites
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The distribution of glass-transition temperatures in nanoscopically confined glass formers
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Effect of Silica Nanoparticles on the Local Segmental Dynamics in Poly(vinyl acetate)
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Immobilized Polymer Layers on Spherical Nanoparticles
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Probing interfacial mobility profiles via the impact of nanoscopic confinement on the strength of the dynamic glass transition
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Polymer Dynamics in PEG-Silica Nanocomposites: Effects of Polymer Molecular Weight, Temperature and Solvent Dilution
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Solid particles in an elastomer matrix: impact of colloid dispersion and polymer mobility modification on the mechanical properties
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Revealed Architectures of Adsorbed Polymer Chains at Solid-Polymer Melt Interfaces
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Combined FTIR and Dielectric Investigation of Poly(vinyl acetate) Adsorbed on Silica Particles
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Segmental Dynamics of Polymer Melts with Spherical Nanoparticles
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Dynamics at the Polymer/Nanoparticle Interface in Poly(2-vinylpyridine)/Silica Nanocomposites
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Evidence for the Shift of the Glass Transition near the Particles in Silica-Filled Elastomers
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Glass Transitions in Highly Attractive Highly Filled Polymer Nanocomposites
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Fragility and cooperative motion in a glass-forming polymer–nanoparticle composite
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Untangling the Effects of Chain Rigidity on the Structure and Dynamics of Strongly Adsorbed Polymer Melts
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Interfacial mobility scale determines the scale of collective motion and relaxation rate in polymer films
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Impact of an Irreversibly Adsorbed Layer on Local Viscosity of Nanoconfined Polymer Melts
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Quantitative equivalence between polymer nanocomposites and thin polymer films
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Interfacial phenomena in core–shell nanocomposites of PDMS adsorbed onto low specific surface area fumed silica nanooxides: Effects of surface modification
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Interfacial dynamics of polydimethylsiloxane adsorbed on fumed metal oxide particles of a wide range of specific surface area
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Densification of Alkoxide-Derived Fine Silica Powder Compact by Ultra-High-Pressure Cold Isostatic Pressing
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Layer-by-Layer Surface Modification of Functional Nanoparticles for Dispersion in Organic Solvents
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An interlayer model for the complex dielectric constant of composites
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Novel Approach to the Analysis of Broadband Dielectric Spectra
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A generalized regularization method for nonlinear ill-posed problems enhanced for nonlinear regularization terms
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Macromolecular Diffusion in a Crowded Polymer Nanocomposite
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Revealing spatially heterogeneous relaxation in a model nanocomposite
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Photo-induced cobalt-mediated radical polymerization of vinyl acetate
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The lifetime of the deviations from bulk behaviour in polymers confined at the nanoscale
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Kinetics of Irreversible Chain Adsorption
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Interphase of a Polymer at a Solid Interface
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Interfacial Free Volume and Vitrification: Reduction in T _g in Proximity of an Adsorbing Interface Explained by the Free Volume Holes Diffusion Model
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Opportunities in theoretical and computational polymeric materials and soft matter
journal, January 2015

Rheological behavior of fumed silica filled polyethylene oxide
journal, February 2019

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

Conformational changes underlying variation in the structural dynamics of materials confined at the nanometric scale
journal, January 2018

Influence of molecular weight on molecular dynamics and dynamic rheology of polypropylene glycol filled with silica
journal, January 2018

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

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

Influence of knot complexity on glass-formation in low molecular mass ring polymer melts
journal, March 2019

Heterogeneous dynamics of unentangled chains in polymer nanocomposites
journal, May 2019

The interfacial zone in thin polymer films and around nanoparticles in polymer nanocomposites
journal, September 2019

Glass transition of polymers in bulk, confined geometries, and near interfaces
journal, January 2017

Effect of Local Chain Conformation in Adsorbed Nanolayers on Confined Polymer Molecular Mobility
journal, May 2019

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

Interfacial Properties and Hopping Diffusion of Small Nanoparticle in Polymer/Nanoparticle Composite with Attractive Interaction on Side Group
journal, May 2018