Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites

Bocharova, Vera; Genix, Anne-Caroline; Carrillo, Jan-Michael Y.; Kumar, Rajeev; Carroll, Bobby; Erwin, Andrew; Voylov, Dmitry; Kisliuk, Alexander; Wang, Yangyang; Sumpter, Bobby G.; Sokolov, Alexei P.

doi:10.1021/acsanm.0c00180

Title: Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites

Abstract

The addition of hard fillers to a polymer matrix is a well-known process for achieving mechanical reinforcement. With a decrease in the size of the fillers, the contribution from polymer–particle nanometer-sized interfaces become significant, and these interfaces affect the mechanical performance of polymer nanocomposites (PNCs) beyond the limits established for conventional composites. However, the molecular mechanisms underlying the improvement in the mechanical performance of glassy PNCs remain unresolved, necessitating a deeper understanding of the structure–property relationships in these intrinsically heterogeneous systems. In this effort, by using Brillouin light scattering (BLS) and dynamic mechanical analysis (DMA), we demonstrated that adding shorter chains to a PNC prepared with high molecular weight polymers significantly improved the mechanical properties of the PNC in the glassy state. The strongest enhancement of mechanical properties occurred at an optimum concentration of short chains. This is in contrast to behavior of the glass transition temperature of PNCs which shows a monotonic decrease with an increase in the concentration of shorter chains. Using experimental data and coarse-grained molecular dynamics (MD) simulations, we have identified the molecular mechanism leading to the observed non-monotonic changes in mechanical reinforcement. Here, this mechanism includes changes in the nanoscale organization at the interface, combinedmore »« less

Authors:

^[1]; Genix, Anne-Caroline ^[2];

^[1];

^[3]; Erwin, Andrew ^[4];

^[3]; Kisliuk, Alexander ^[1];

^[1];

^[5]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. de Montpellier (France)
Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Georgia Tech, Atlanta, GA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Publication Date:: Mon Mar 23 00:00:00 EDT 2020

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). Materials Sciences & Engineering Division

OSTI Identifier:: 1608195

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Nano Materials

Additional Journal Information:: Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 2574-0970

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer nanocomposites; mechanical reinforcement; glass transition; segmental dynamics; interfacial layer; nonequilibrium; interfaces; layers; nanoparticles; nanocomposites; polymers

Citation Formats


                    Bocharova, Vera, Genix, Anne-Caroline, Carrillo, Jan-Michael Y., Kumar, Rajeev, Carroll, Bobby, Erwin, Andrew, Voylov, Dmitry, Kisliuk, Alexander, Wang, Yangyang, Sumpter, Bobby G., and Sokolov, Alexei P. Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites.  United States: N. p., 2020. 
Web.  doi:10.1021/acsanm.0c00180.

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                    Bocharova, Vera, Genix, Anne-Caroline, Carrillo, Jan-Michael Y., Kumar, Rajeev, Carroll, Bobby, Erwin, Andrew, Voylov, Dmitry, Kisliuk, Alexander, Wang, Yangyang, Sumpter, Bobby G., & Sokolov, Alexei P. Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites.  United States.  https://doi.org/10.1021/acsanm.0c00180

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                    Bocharova, Vera, Genix, Anne-Caroline, Carrillo, Jan-Michael Y., Kumar, Rajeev, Carroll, Bobby, Erwin, Andrew, Voylov, Dmitry, Kisliuk, Alexander, Wang, Yangyang, Sumpter, Bobby G., and Sokolov, Alexei P. Mon .  
"Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites".  United States.  https://doi.org/10.1021/acsanm.0c00180.  https://www.osti.gov/servlets/purl/1608195.

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@article{osti_1608195,

  title        = {Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites},

  author       = {Bocharova, Vera and Genix, Anne-Caroline and Carrillo, Jan-Michael Y. and Kumar, Rajeev and Carroll, Bobby and Erwin, Andrew and Voylov, Dmitry and Kisliuk, Alexander and Wang, Yangyang and Sumpter, Bobby G. and Sokolov, Alexei P.},

  abstractNote = {The addition of hard fillers to a polymer matrix is a well-known process for achieving mechanical reinforcement. With a decrease in the size of the fillers, the contribution from polymer–particle nanometer-sized interfaces become significant, and these interfaces affect the mechanical performance of polymer nanocomposites (PNCs) beyond the limits established for conventional composites. However, the molecular mechanisms underlying the improvement in the mechanical performance of glassy PNCs remain unresolved, necessitating a deeper understanding of the structure–property relationships in these intrinsically heterogeneous systems. In this effort, by using Brillouin light scattering (BLS) and dynamic mechanical analysis (DMA), we demonstrated that adding shorter chains to a PNC prepared with high molecular weight polymers significantly improved the mechanical properties of the PNC in the glassy state. The strongest enhancement of mechanical properties occurred at an optimum concentration of short chains. This is in contrast to behavior of the glass transition temperature of PNCs which shows a monotonic decrease with an increase in the concentration of shorter chains. Using experimental data and coarse-grained molecular dynamics (MD) simulations, we have identified the molecular mechanism leading to the observed non-monotonic changes in mechanical reinforcement. Here, this mechanism includes changes in the nanoscale organization at the interface, combined with chain stretching amplified by the addition of the short chains. Overall, our approach paves a simple, cost-effective pathway to fabricating glassy PNCs with significantly improved mechanical properties that will fill various practical needs.},

  doi          = {10.1021/acsanm.0c00180},

  journal      = {ACS Applied Nano Materials},

  number       = 4,

  volume       = 3,

  place        = {United States},

  year         = {Mon Mar 23 00:00:00 EDT 2020},

  month        = {Mon Mar 23 00:00:00 EDT 2020}

}

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Significant changes in materials properties of siloxane based polymers can be obtained by the addition of inorganic fillers. In silica-filled polydimethylsiloxane (PDMS) based composites the mechanism of this reinforcing behavior is presumably hydrogen bonding between surface hydroxyls and backbone siloxane species. We have chosen to investigate in detail the effect of chemisorbed and physisorbed water on the interfacial structure and dynamics in silica-filled PDMS based composites. Toward this end, we have combined molecular dynamics simulations and experimental studies employing DMA and Nh4R analysis. Our results suggest that the polymer-silica contact distance and the mobility of interfacial polymer chains significantly decreasedmore »« less
https://doi.org/10.1557/PROC-710-DD4.2.1

Full Text Available
Structural and Dynamical Roles of Bound Polymer Chains in Rubber Reinforcement

Journal Article Salatto, Daniel ; Carrillo, Jan-Michael Y. ; Endoh, Maya K. ; ... - Macromolecules

The addition of nanofillers to rubber matrices is a powerful route to improve the mechanical properties. Here, we focus on a molecular understanding of basic mechanisms that are important for the reinforcement in rubbers. The key role in this process is ascribed to bound rubber (BR) that engages with the matrix as well as with adjacent nanofillers. To date, this understanding has been impeded by the lack of experimental tools to directly probe the BR chains buried in a polymer matrix composed of the same polymer. To tackle this challenge, we combine neutron scattering/spectroscopy techniques with isotope-labeling and molecular dynamicsmore »« less
https://doi.org/10.1021/acs.macromol.1c01239

Full Text Available

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Title: Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites

Abstract

Citation Formats

Transparent BaTiO 3 /PMMA Nanocomposite Films for Display Technologies: Facile Surface Modification Approach for BaTiO 3 Nanoparticles journal, April 2018

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

Thermal conductivity of carbon nanotubes and their polymer nanocomposites: A review journal, July 2011

Enhancement of Mechanical and Thermal Properties of Polycaprolactone/Chitosan Blend by Calcium Carbonate Nanoparticles journal, April 2012

Tailoring the Refractive Indices of Thin Film Polymer Metallic Nanoparticle Nanocomposites journal, June 2012

Nanoparticle Polymer Composites: Where Two Small Worlds Meet journal, November 2006

50th Anniversary Perspective : Are Polymer Nanocomposites Practical for Applications? journal, January 2017

Particle size dependence of the Young's modulus of filled polymers: 1. Preliminary experiments journal, September 1989

Tensile performance improvement of low nanoparticles filled-polypropylene composites journal, August 2002

An interface model for the prediction of Young's modulus of layered silicate-elastomer nanocomposites journal, October 1998

Enhancing the Mechanical Properties of Glassy Nanocomposites by Tuning Polymer Molecular Weight journal, September 2018

Structure and properties of polyurethane-silica nanocomposites journal, April 2000

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

The filler–rubber interface in styrene butadiene nanocomposites with anisotropic silica particles: morphology and dynamic properties journal, January 2015

Immobilized Polymer Layers on Spherical Nanoparticles journal, April 2010

Effects of Molecular Weight below the Entanglement Threshold on Interfacial Nanoparticles/Polymer Dynamics journal, December 2016

Interfacial Interactions and Segmental Dynamics of Poly(vinyl acetate)/Silica Nanocomposites journal, May 2015

Morphology, Molecular Dynamics, and Interfacial Phenomena in Systems Based on Silica Modified by Grafting Polydimethylsiloxane Chains and Physically Adsorbed Polydimethylsiloxane journal, March 2019

Theory of Filler Reinforcement journal, January 1945

Perspective: Outstanding theoretical questions in polymer-nanoparticle hybrids journal, July 2017

Microfibrillar reinforced composites from PET/PP blends: processing, morphology and mechanical properties journal, January 2005

Nanofibril reinforced composites from polymer blends journal, February 2008

Self-formation of elastomer network assisted by nano-silicon dioxide particles: A simple and efficient route toward polymer nanocomposites with simultaneous improved toughness and stiffness journal, February 2016

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

Enhanced Glassy State Mechanical Properties of Polymer Nanocomposites via Supramolecular Interactions journal, July 2015

Nanocomposites with Polymer Grafted Nanoparticles journal, April 2013

Investigation of the fracture mechanism and mechanical properties of polystyrene/silica nanocomposite in various silica contents journal, September 2011

Thermomechanical Properties of Bimodal Brush Modified Nanoparticle Composites journal, June 2013

Mechanical properties of polymer grafted nanoparticle composites journal, October 2018

Influence of nanoparticle size, loading, and shape on the mechanical properties of polymer nanocomposites journal, December 2012

Polymer Layered Silicate Nanocomposites: A Review journal, August 2009

The effect of nanoparticle shape on polymer-nanocomposite rheology and tensile strength journal, January 2007

Role of Filler Shape and Connectivity on the Viscoelastic Behavior in Polymer Nanocomposites journal, July 2015

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

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

Gradient of glass transition temperature in filled elastomers journal, October 2003

Anisotropic self-assembly of spherical polymer-grafted nanoparticles journal, March 2009

“Gel-like” Mechanical Reinforcement in Polymer Nanocomposite Melts journal, January 2010

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

Network dynamics in nanofilled polymers journal, April 2016

Mechanical Reinforcement of Polymer Nanocomposites from Percolation of a Nanoparticle Network journal, March 2015

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

How Melt-Stretching Affects Mechanical Behavior of Polymer Glasses journal, July 2012

A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses journal, September 2014

Spectrum of fast dynamics in glass forming liquids: Does the “knee” exist? journal, February 1999

Measurement of the Young's modulus of Nafion membranes by Brillouin light scattering journal, December 2010

Contact Aggregation, Bridging, and Steric Stabilization in Dense Polymer−Particle Mixtures journal, October 2005

Molecular theories of polymer nanocomposites journal, April 2010

High resolution XPS of organic polymers, the scienta ESCA300 database. By G. Beamson and D. Briggs, Wiley, Chichester 1992, 295 pp., hardcover, £ 65.00, ISBN 0-471-93592-1 journal, October 1993

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites journal, January 2017

Experimental and theoretical study of the N1s and C1s shake-up satellites in pyridine and aniline journal, September 1991

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

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

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

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

Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers journal, February 2019

Surface segregation in binary polymer mixtures: a lattice model journal, August 1991

Kinetics of Competitive Adsorption of PEO Chains with Different Molecular Weights journal, October 1998

Dynamics in adsorbed homopolymer layers: Understanding complexity from simple starting points journal, October 2005

Morphology Control in Solution-Processed Bulk-Heterojunction Solar Cell Mixtures journal, October 2009

New Mechanism of Nonequilibrium Polymer Adsorption journal, February 1992

Statistical theory of the adsorption of interacting chain molecules. 2. Train, loop, and tail size distribution journal, January 1980

Analytical Approximation to the Scheutjens−Fleer Theory for Polymer Adsorption from Dilute Solution. 1. Trains, Loops, and Tails in Terms of Two Parameters: The Proximal and Distal Lengths journal, February 1999

Infrared Study of the Kinetics and Mechanism of Adsorption of Acrylic Polymers on Alumina Surfaces journal, May 2004

Nanoscale adsorbed structures as a robust approach for tailoring polymer film stability journal, January 2016

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

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

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

Implementing molecular dynamics on hybrid high performance computers – short range forces journal, April 2011

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

Universal Viscosity Behavior of Polymer Nanocomposites journal, November 2012

Transparent BaTiO ₃ /PMMA Nanocomposite Films for Display Technologies: Facile Surface Modification Approach for BaTiO ₃ Nanoparticles
journal, April 2018

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

Thermal conductivity of carbon nanotubes and their polymer nanocomposites: A review
journal, July 2011

Enhancement of Mechanical and Thermal Properties of Polycaprolactone/Chitosan Blend by Calcium Carbonate Nanoparticles
journal, April 2012

Tailoring the Refractive Indices of Thin Film Polymer Metallic Nanoparticle Nanocomposites
journal, June 2012

Nanoparticle Polymer Composites: Where Two Small Worlds Meet
journal, November 2006

50th Anniversary Perspective : Are Polymer Nanocomposites Practical for Applications?
journal, January 2017

Particle size dependence of the Young's modulus of filled polymers: 1. Preliminary experiments
journal, September 1989

Tensile performance improvement of low nanoparticles filled-polypropylene composites
journal, August 2002

An interface model for the prediction of Young's modulus of layered silicate-elastomer nanocomposites
journal, October 1998

Enhancing the Mechanical Properties of Glassy Nanocomposites by Tuning Polymer Molecular Weight
journal, September 2018

Structure and properties of polyurethane-silica nanocomposites
journal, April 2000

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

The filler–rubber interface in styrene butadiene nanocomposites with anisotropic silica particles: morphology and dynamic properties
journal, January 2015

Immobilized Polymer Layers on Spherical Nanoparticles
journal, April 2010

Effects of Molecular Weight below the Entanglement Threshold on Interfacial Nanoparticles/Polymer Dynamics
journal, December 2016

Interfacial Interactions and Segmental Dynamics of Poly(vinyl acetate)/Silica Nanocomposites
journal, May 2015

Morphology, Molecular Dynamics, and Interfacial Phenomena in Systems Based on Silica Modified by Grafting Polydimethylsiloxane Chains and Physically Adsorbed Polydimethylsiloxane
journal, March 2019

Theory of Filler Reinforcement
journal, January 1945

Perspective: Outstanding theoretical questions in polymer-nanoparticle hybrids
journal, July 2017

Microfibrillar reinforced composites from PET/PP blends: processing, morphology and mechanical properties
journal, January 2005

Nanofibril reinforced composites from polymer blends
journal, February 2008

Self-formation of elastomer network assisted by nano-silicon dioxide particles: A simple and efficient route toward polymer nanocomposites with simultaneous improved toughness and stiffness
journal, February 2016

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

Enhanced Glassy State Mechanical Properties of Polymer Nanocomposites via Supramolecular Interactions
journal, July 2015

Nanocomposites with Polymer Grafted Nanoparticles
journal, April 2013

Investigation of the fracture mechanism and mechanical properties of polystyrene/silica nanocomposite in various silica contents
journal, September 2011

Thermomechanical Properties of Bimodal Brush Modified Nanoparticle Composites
journal, June 2013

Mechanical properties of polymer grafted nanoparticle composites
journal, October 2018

Influence of nanoparticle size, loading, and shape on the mechanical properties of polymer nanocomposites
journal, December 2012

Polymer Layered Silicate Nanocomposites: A Review
journal, August 2009

The effect of nanoparticle shape on polymer-nanocomposite rheology and tensile strength
journal, January 2007

Role of Filler Shape and Connectivity on the Viscoelastic Behavior in Polymer Nanocomposites
journal, July 2015

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

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

Gradient of glass transition temperature in filled elastomers
journal, October 2003

Anisotropic self-assembly of spherical polymer-grafted nanoparticles
journal, March 2009

“Gel-like” Mechanical Reinforcement in Polymer Nanocomposite Melts
journal, January 2010

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

Network dynamics in nanofilled polymers
journal, April 2016

Mechanical Reinforcement of Polymer Nanocomposites from Percolation of a Nanoparticle Network
journal, March 2015

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

How Melt-Stretching Affects Mechanical Behavior of Polymer Glasses
journal, July 2012

A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses
journal, September 2014

Spectrum of fast dynamics in glass forming liquids: Does the “knee” exist?
journal, February 1999

Measurement of the Young's modulus of Nafion membranes by Brillouin light scattering
journal, December 2010

Contact Aggregation, Bridging, and Steric Stabilization in Dense Polymer−Particle Mixtures
journal, October 2005

Molecular theories of polymer nanocomposites
journal, April 2010

High resolution XPS of organic polymers, the scienta ESCA300 database. By G. Beamson and D. Briggs, Wiley, Chichester 1992, 295 pp., hardcover, £ 65.00, ISBN 0-471-93592-1
journal, October 1993

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites
journal, January 2017

Experimental and theoretical study of the N1s and C1s shake-up satellites in pyridine and aniline
journal, September 1991

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

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

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

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

Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers
journal, February 2019

Surface segregation in binary polymer mixtures: a lattice model
journal, August 1991

Kinetics of Competitive Adsorption of PEO Chains with Different Molecular Weights
journal, October 1998

Dynamics in adsorbed homopolymer layers: Understanding complexity from simple starting points
journal, October 2005

Morphology Control in Solution-Processed Bulk-Heterojunction Solar Cell Mixtures
journal, October 2009

New Mechanism of Nonequilibrium Polymer Adsorption
journal, February 1992

Statistical theory of the adsorption of interacting chain molecules. 2. Train, loop, and tail size distribution
journal, January 1980

Analytical Approximation to the Scheutjens−Fleer Theory for Polymer Adsorption from Dilute Solution. 1. Trains, Loops, and Tails in Terms of Two Parameters: The Proximal and Distal Lengths
journal, February 1999

Infrared Study of the Kinetics and Mechanism of Adsorption of Acrylic Polymers on Alumina Surfaces
journal, May 2004

Nanoscale adsorbed structures as a robust approach for tailoring polymer film stability
journal, January 2016

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

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

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

Implementing molecular dynamics on hybrid high performance computers – short range forces
journal, April 2011

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

Universal Viscosity Behavior of Polymer Nanocomposites
journal, November 2012