A Unified Approach to Disjoining Pressure in Liquid and Vapor Interlayer within the Framework of the Density Functional Theory

Abstract

The classical density functional theory makes it possible to explicitly calculate the local density profiles, the components of the pressure tensor, and the thicknesses of thin interlayers between a lyophilic or lyophobic solid surface and, accordingly, gas or liquid phases at different values of the chemical potentials of the phases. Within the framework of a unified approach based on the gradient approximation of the classical density functional theory, it has been shown that, at certain values of parameters characterizing the wettability or nonwettability of a solid, equilibrium liquid films or vapor layers of a uniform thickness are formed around a spherical particle, if its surface is lyophilic or lyophobic, respectively. Mechanical and thermodynamic definitions have been given for the disjoining pressure in the spherical liquid or vapor interlayer around a solid particle, and the agreement between the definitions has been proven by calculations at different interlayer thicknesses and particle radii. It has been shown that the disjoining pressure in a vapor interlayer around a nanosized lyophobic particle decreases with an increase in particle radius, with this phenomenon being opposite to the situation with liquid films.