Fluids density functional theory studies of supramolecular polymers at a hard surface

Fluids density functional theory studies of supramolecular polymers at a hard surface

McGarrity, E.S.
Thijssen, J.M.
Besseling, N.A.M.

Mechanical, Maritime and Materials Engineering

Process and Energy

2010-08-26

We have applied a fluids density functional theory based on that of Yu and Wu [J. Chem. Phys. 116, 7094 (2002)] to treat reversible supramolecular polymers near a hard surface. This approach combines a hard-sphere fluids density functional theory with the first-order thermodynamic perturbation theory of Wertheim. The supramolecular polymers are represented in the theory by hard-spheres with two associating sites. We explore the effects of the bonding scheme, monomer concentration, and association energy upon the equilibrium chain sizes and the depletion lengths. This study is performed on simple systems containing two-site monomers and binary mixtures of two-site monomers combined with end stopper monomers which have only a single association site. Our model has correct behavior in the dilute and overlap regimes and the bulk results can be easily connected to simpler random-flight models. We find that there is a nonmonotonic behavior of the depletion length of the polymers as a function of concentration and that this depletion length can be controlled through the concentration of end stoppers. These results are applicable to the study of colloidal dispersions in supramolecular polymer solutions.

bonds (chemical)
density functional theory
perturbation theory
polymers
thermodynamics

http://resolver.tudelft.nl/uuid:65ab9c19-a113-4bb3-a855-c42d483d51fe

https://doi.org/10.1063/1.3469789

American Institute of Physics

0021-9606

http://link.aip.org/link/JCPSA6/v133/i8/p084902/s1

Journal of Chemical Physics, 133 (8), 2010

Institutional Repository

journal article

(c) 2010 The Author(s); American Institute of Physics