Connecting Colloidal Forces to the Equilibrium Thickness of Particulate Deposits on a Substrate in Contact with a Suspension Using Classical Density Functional Theory

Langmuir. 2023 Apr 25;39(16):5689-5696. doi: 10.1021/acs.langmuir.2c03374. Epub 2023 Apr 10.

Abstract

We study contributions of colloidal forces, i.e., hydrophobic, van der Waals, and electrical double layer interactions, to the thickness of a colloidal deposit in equilibrium with an aqueous suspension by using classical density functional theory, which we expand to obtain a Ginzburg-Landau type energy functional. We regard colloidal particles as clusters of molecular segments-a reminiscent of polymer statistical physics and of the classic Hamaker treatment of van der Waals interactions between particles. This approach appropriately accounts for the integral interaction energy between colloidal particles, which may take magnitudes of many times the characteristic molecular thermal energy kBT (Boltzmann constant times temperature). The analysis highlights the well-known insight that entropy is mostly governed by the solvent molecules and gives physical values to the statistical coefficients in a Ginzburg-Landau type energy functional.