Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites

Martin, Halie J.; White, B. Tyler; Yuan, Guangcui; Saito, Tomonori; Dadmun, Mark D.

doi:10.1021/acs.macromol.8b02596

Title: Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites

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Abstract

The dynamics of polymers in an all-polymer nanocomposite that are composed of soft cross-linked polystyrene nanoparticles and linear polystyrene have been examined. In this article, we describe how the relative size of the nanoparticle to that of the polymer chain and its rigidity impact the linear polymer chain diffusion. The results of the in situ neutron reflectivity experiments show three distinct regimes in the linear polymer diffusion. The results indicate that the inclusion of soft nanoparticles increases the amount of topological constraints and confinement effects for low matrix molecular weight polymer. At modest molecular weights where the size of the nanoparticle and polymer chain are similar, the soft nanoparticles neither inhibit nor enhance the linear polymer diffusion, while at the highest polymer matrix molecular weight, the linear polymer diffusion increases due to an increase in the constraint release mechanism by the soft nanoparticles. Thermal analysis demonstrates that the nanoparticles do not increase the free volume of the system nor do they behave as a plasticizing agent. These results are interpreted to indicate that the competition between a topological barrier effect and enhancing constraint release defines the behavior of a given all-polymer nanocomposite.

Authors:

Martin, Halie J. ^[1];

^[2]; Yuan, Guangcui ^[3];

^[2];

^[4]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Georgetown, Washington, DC (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: 2019-03-26

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:: 1505300

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 52; Journal Issue: 7; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats


                    Martin, Halie J., White, B. Tyler, Yuan, Guangcui, Saito, Tomonori, and Dadmun, Mark D.. Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.macromol.8b02596.

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                    Martin, Halie J., White, B. Tyler, Yuan, Guangcui, Saito, Tomonori, & Dadmun, Mark D.. Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites.  United States.  https://doi.org/10.1021/acs.macromol.8b02596

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                    Martin, Halie J., White, B. Tyler, Yuan, Guangcui, Saito, Tomonori, and Dadmun, Mark D.. Tue .  
"Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites".  United States.  https://doi.org/10.1021/acs.macromol.8b02596.  https://www.osti.gov/servlets/purl/1505300.

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@article{osti_1505300,

  title        = {Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites},

  author       = {Martin, Halie J. and White, B. Tyler and Yuan, Guangcui and Saito, Tomonori and Dadmun, Mark D.},

  abstractNote = {The dynamics of polymers in an all-polymer nanocomposite that are composed of soft cross-linked polystyrene nanoparticles and linear polystyrene have been examined. In this article, we describe how the relative size of the nanoparticle to that of the polymer chain and its rigidity impact the linear polymer chain diffusion. The results of the in situ neutron reflectivity experiments show three distinct regimes in the linear polymer diffusion. The results indicate that the inclusion of soft nanoparticles increases the amount of topological constraints and confinement effects for low matrix molecular weight polymer. At modest molecular weights where the size of the nanoparticle and polymer chain are similar, the soft nanoparticles neither inhibit nor enhance the linear polymer diffusion, while at the highest polymer matrix molecular weight, the linear polymer diffusion increases due to an increase in the constraint release mechanism by the soft nanoparticles. Thermal analysis demonstrates that the nanoparticles do not increase the free volume of the system nor do they behave as a plasticizing agent. These results are interpreted to indicate that the competition between a topological barrier effect and enhancing constraint release defines the behavior of a given all-polymer nanocomposite.},

  doi          = {10.1021/acs.macromol.8b02596},

  journal      = {Macromolecules},

  number       = 7,

  volume       = 52,

  place        = {United States},

  year         = {2019},

  month        = {3}

}

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