Diffusion of Sticky Nanoparticles in a Polymer Melt: Crossover from Suppressed to Enhanced Transport

Bobby Carroll; Vera Bocharova; Jan Michael Y. Carrillo; Alexander Kisliuk; Shiwang Cheng; Umi Yamamoto; Kenneth S. Schweizer; Bobby G. Sumpter; Alexei P. Sokolov

doi:10.1021/acs.macromol.7b02695

Diffusion of Sticky Nanoparticles in a Polymer Melt: Crossover from Suppressed to Enhanced Transport

Bobby Carroll, Vera Bocharova, Jan Michael Y. Carrillo, Alexander Kisliuk, Shiwang Cheng, Umi Yamamoto, Kenneth S. Schweizer, Bobby G. Sumpter, Alexei P. Sokolov

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58 Scopus citations

Abstract

The self-diffusion of a single large particle in a fluid is usually described by the classic Stokes-Einstein (SE) hydrodynamic relation. However, there are many fluids where the SE prediction for nanoparticles diffusion fails. These systems include diffusion of nanoparticles in porous media, in entangled and unentangled polymer melts and solutions, and protein diffusion in biological environments. A fundamental understanding of the microscopic parameters that govern nanoparticle diffusion is relevant to a wide range of applications. In this work, we present experimental measurements of the tracer diffusion coefficient of small and large nanoparticles that experience strong attractions with unentangled and entangled polymer melt matrices. For the small nanoparticle system, a crossover from suppressed to enhanced diffusion is observed with increasing polymer molecular weight. We interpret these observations based on our theoretical and simulation insights of the preceding article (paper 1) as a result of a crossover from an effective hydrodynamic core-shell to a nonhydrodynamic vehicle mechanism of transport, with the latter strongly dependent on polymer-nanoparticle desorption time. A general zeroth-order qualitative picture for small sticky nanoparticle diffusion in polymer melts is proposed.

Original language	English
Pages (from-to)	2268-2275
Number of pages	8
Journal	Macromolecules
Volume	51
Issue number	6
DOIs	https://doi.org/10.1021/acs.macromol.7b02695
State	Published - Mar 27 2018

Funding

This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. Simulations were performed at the Center for Nanophase Materials Sciences, which is a US Department of Energy Office of Science User Facility. This research also used resources of the Oak Ridge Leadership Computing Facility at Oak Ridge National Laboratory, which is supported by the Office of Science of the Department of Energy under Contract DE-AC05-00OR22725. This work was supported by the U.S. Department of Energy Office of Science, Basic Energy Sciences, Materials Science and Engineering Division. Simulations were performed at the Center for Nanophase Materials Sciences, which is a US Department of Energy Office of Science User Facility. This research also used resources of the Oak Ridge Leadership Computing Facility at Oak Ridge National Laboratory, which is supported by the Office of Science of the Department of Energy under Contract DE-AC05-00OR22725.

Funders	Funder number
Materials Science and Engineering Division
Office of Science of the Department of Energy	DE-AC05-00OR22725
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory

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title = "Diffusion of Sticky Nanoparticles in a Polymer Melt: Crossover from Suppressed to Enhanced Transport",

abstract = "The self-diffusion of a single large particle in a fluid is usually described by the classic Stokes-Einstein (SE) hydrodynamic relation. However, there are many fluids where the SE prediction for nanoparticles diffusion fails. These systems include diffusion of nanoparticles in porous media, in entangled and unentangled polymer melts and solutions, and protein diffusion in biological environments. A fundamental understanding of the microscopic parameters that govern nanoparticle diffusion is relevant to a wide range of applications. In this work, we present experimental measurements of the tracer diffusion coefficient of small and large nanoparticles that experience strong attractions with unentangled and entangled polymer melt matrices. For the small nanoparticle system, a crossover from suppressed to enhanced diffusion is observed with increasing polymer molecular weight. We interpret these observations based on our theoretical and simulation insights of the preceding article (paper 1) as a result of a crossover from an effective hydrodynamic core-shell to a nonhydrodynamic vehicle mechanism of transport, with the latter strongly dependent on polymer-nanoparticle desorption time. A general zeroth-order qualitative picture for small sticky nanoparticle diffusion in polymer melts is proposed.",

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AU - Cheng, Shiwang

AU - Yamamoto, Umi

AU - Schweizer, Kenneth S.

AU - Sumpter, Bobby G.

AU - Sokolov, Alexei P.

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Diffusion of Sticky Nanoparticles in a Polymer Melt: Crossover from Suppressed to Enhanced Transport

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