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Dynamics of Solvent-free Grafted Nanoparticles

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Abstract

The diffusivity and structural relaxation characteristics of oligomer-grafted nanoparticles have been investigated with simulations of a previously proposed coarse-grained model at atmospheric pressure. Solvent-free, polymer-grafted nanoparticles as well as grafted nanoparticles in a melt were compared to a reference system of bare (ungrafted) particles in a melt. Whereas longer chains lead to a larger hydrodynamic radius and lower relative diffusivity for grafted particles in a melt, bulk solvent-free nanoparticles with longer chains have higher relative diffusivities than their short chain counterparts. Solvent-free nanoparticles with short chains undergo a glass transition as indicated by a vanishing diffusivity, diverging structural relaxation time and the formation of body-centered-cubic-like order. Nanoparticles with longer chains exhibit a more gradual increase in the structural relaxation time with decreasing temperature and concomitantly increasing particle volume fraction. The diffusivity of the long chain nanoparticles exhibits a minimum at an intermediate temperature and volume fraction where the polymer brushes of neighboring particles overlap, but must stretch to fill the interparticle space.

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The authors would like to thank Professor Fernando Escobedo and Hsiu-Yu Yu for helpful discussions and Professor Escobedo for suggesting the simulation model used in this work. This publication is based on work supported in part by Award No.KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). Additional support was provided by grant CBET-1033155 from the U.S. National Science Foundation (NSF).

Date Issued

2012-01-26

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The Journal of Chemical Physics

Keywords

oligomer-grafted nanoparticles; polymer-grafted nanoparticles; nanoparticles with longer chains

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Chremos, Alexandros, Athanassios Z. Panagiotopoulos, and Donald L. Koch. "Dynamics of Solvent-free Grafted Nanoparticles." The Journal of Chemical Physics 136.4 (2012): 044902. Web.

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