Spatially dependent relative diffusion of nanoparticles in polymer melts

Umi Yamamoto, Kenneth S. Schweizer

Research output: Contribution to journalArticlepeer-review

Abstract

We formulate and apply a microscopic statistical-mechanical theory for the non-hydrodynamic relative diffusion coefficient of a pair of spherical nanoparticles in entangled polymer melts based on a combination of Brownian motion, mode-coupling, and polymer physics ideas. The focus is on the mesoscopic regime where particles are larger than the entanglement spacing. The dependence of the non-hydrodynamic friction on interparticle separation, degree of entanglement, and tube diameter is systematically studied. The overall magnitude of the relative diffusivity is controlled by the ratio of the particle to tube diameter and the number of entanglements in a manner reminiscent of single-particle self-diffusion and Stokes-Einstein violations. A rich spatial separation dependence of mobility enhancement relative to the hydrodynamic behavior is predicted even for very large particles, and the asymptotic dependence is derived analytically in the small and large separation limits. Particle separations in excess of 100 nm are sometimes required to recover the hydrody-namic limit. The effects of local polymer-particle packing correlations are found to be weak, and the non-hydrodynamic effects are also small for unentangled melts.

Original languageEnglish (US)
Article number064907
JournalJournal of Chemical Physics
Volume139
Issue number6
DOIs
StatePublished - Aug 14 2013

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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