Issue 16, 2013

Anomalous diffusion in polymer monolayers

Abstract

The tagged chain dynamics in strictly two-dimensional (2D) polymer melts (where the chains are collapsed to dense spots) is considered both theoretically and by computer simulations. It is shown that the chain relaxation time in such systems scales as tmNα with α ≈ 1.73 (N is the number of monomer units per chain). An extended transient regime of anomalous subdiffusion is identified at ttm where the chain centre-of-mass (CM) velocity autocorrelation function (VAF) scales as C(t) ∝ −N0t−1.42. This anomalous dynamics is accounted for by the effect of the viscoelastic hydrodynamic interactions (VHI). The developed quantitative theory of the VHI-controlled chain dynamics is in good agreement, with no parameter adjustment, with the extensive simulation data. The dynamics of polymer monolayers with frictional contact to the supporting surface is considered as well. It is shown that an external (Langevin) friction γ leads to the asymptotic regime C(t) ∝ −()−1.37t−0.84 that crosses over to −N0t−1.42 at longer t. We also present a detailed analysis of other important factors controlling the 2D chain diffusion: finite box-size, inertial and finite compressibility effects.

Graphical abstract: Anomalous diffusion in polymer monolayers

Article information

Article type
Paper
Submitted
11 Dec 2012
Accepted
24 Jan 2013
First published
12 Mar 2013

Soft Matter, 2013,9, 4249-4272

Anomalous diffusion in polymer monolayers

A. N. Semenov and H. Meyer, Soft Matter, 2013, 9, 4249 DOI: 10.1039/C3SM27839E

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