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Title: Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

Abstract

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling of NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior.more » In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2];  [5]
  1. Univ. of Illinois, Urbana, IL (United States). Dept. of Physics; California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  5. Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Materials Science, Dept. of Chemistry, and Frederick Seitz Materials Research Lab.
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1430614
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 6; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Yamamoto, Umi, Carrillo, Jan-Michael Y., Bocharova, Vera, Sokolov, Alexei P., Sumpter, Bobby G., and Schweizer, Kenneth. Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.7b02694.
Yamamoto, Umi, Carrillo, Jan-Michael Y., Bocharova, Vera, Sokolov, Alexei P., Sumpter, Bobby G., & Schweizer, Kenneth. Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts. United States. doi:10.1021/acs.macromol.7b02694.
Yamamoto, Umi, Carrillo, Jan-Michael Y., Bocharova, Vera, Sokolov, Alexei P., Sumpter, Bobby G., and Schweizer, Kenneth. Tue . "Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts". United States. doi:10.1021/acs.macromol.7b02694. https://www.osti.gov/servlets/purl/1430614.
@article{osti_1430614,
title = {Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts},
author = {Yamamoto, Umi and Carrillo, Jan-Michael Y. and Bocharova, Vera and Sokolov, Alexei P. and Sumpter, Bobby G. and Schweizer, Kenneth},
abstractNote = {We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling of NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.},
doi = {10.1021/acs.macromol.7b02694},
journal = {Macromolecules},
number = 6,
volume = 51,
place = {United States},
year = {2018},
month = {3}
}

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