Polydisperse polymers near a solid surface: Analytical mean-field theory

A A. F. den Ouden (Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,) R R. Tuinier (Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,) M M. Vis (Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,) C C. M. Martens (Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,)

Abstract

A linearized mean-field theory is presented, which provides algebraic expressions for the segment density profiles and surface tension of polydisperse polymers near a flat surface. The main finding is that surface properties of polydisperse polymers in solution are well-described by the average degree of polymerization N̄, independent of the shape or variance σ2 of the chain length distribution. Polymers with longer chain lengths are found to preferentially adsorb at the surface in the weak adsorption regime. Analytical expressions are derived for the adsorbed amount and surface tension. The results are in quantitative agreement with numerical self-consistent field computations, as long as the ratio σ2/N̄3 is small compared to the static structure factor of Gaussian chains. The analytical expressions are shown to be valid for polymer solutions and for polymer melts. For the case of polymer melts, we show that our theoretical predictions are in agreement with experimental results.

Article Details

Volume / Issue Vol. 163, Issue 6
Published August 14, 2025
ISSN 0021-9606
Publisher American Institute of Physics

Journal Info

The Journal of Chemical Physics

American Institute of Physics

ISSN: 0021-9606 Physical Sciences

Authors (4)

A

A. F. den Ouden

Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,

R

R. Tuinier

Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,

M

M. Vis

Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,

C

C. M. Martens

Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology 1 , P.O. Box 513, 5600 MB Eindhoven,