Concentration-induced planar-to-homeotropic anchoring transition of stiff ring polymers on hard walls

Author(s)
Peter Poier, Sergei A. Egorov, Christos N. Likos, Ronald Blaak
Abstract

We study the structure and interfacial ordering of stiff ring polymers close to repulsive walls. For this purpose, we employ an anisotropic effective model in which the rings are pictured as soft, penetrable discs [P. Poier, C. N. Likos, A. J. Moreno and R. Blaak, Macromolecules, 2015, 48, 4983]. We have studied this model in the bulk and in the presence of a wall, employing Density Functional Theory and computer simulations. While the Ornstein-Zernike equation in combination with the Hypernetted Chain Approximation gives results that are in quantitative agreement with computer simulations, a simple Mean Field approximation strongly overestimates the interaction between the effective particles in the bulk. We discover that by increasing density one can induce a reorientation of the effective rings in the vicinity of a wall, which prefer to orient themselves parallel to the surface (face-on or planar) for low densities ρ and reorient orthogonal to the wall (edge-on or homeotropic) for higher values of ρ. This transition in the surface-structure can be observed in both computer simulations, as well as in an appropriate density functional theory. We trace its physical origin in the penetrable character of the rings, which allows for a reduction of the surface tension contribution due to ring-ring interactions upon the emergence of homeotropic ordering on the wall and increasing the density of the system.

Organisation(s)
Computational and Soft Matter Physics, Research Platform Erwin Schrödinger International Institute for Mathematics and Physics
Journal
Soft Matter
Volume
12
Pages
7983-7994
No. of pages
12
ISSN
1744-683X
DOI
https://doi.org/10.1039/c6sm01453d
Publication date
2016
Peer reviewed
Yes
Austrian Fields of Science 2012
103015 Condensed matter
Keywords
ASJC Scopus subject areas
Condensed Matter Physics, General Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/37f6d079-2e61-48fd-bf67-5959090878ed