Capillary rise between planar surfaces

Minimization of free energy is used to calculate the equilibrium vertical rise and meniscus shape of a liquid column between two closely spaced, parallel planar surfaces that are inert and immobile. States of minimum free energy are found using standard variational principles, which lead not only to an Euler-Lagrange differential equation for the meniscus shape and elevation, but also to the boundary conditions at the three-phase junction where the liquid meniscus intersects the solid walls. The analysis shows that the classical Young-Dupre equation for the thermodynamic contact angle is valid at the three-phase junction, as already shown for sessile drops with or without the influence of a gravitational field. Integration of the Euler-Lagrange equation shows that a generalized Laplace-Young (LY) equation first proposed by O'Brien, Craig, and Peyton [J. Colloid Interface Sci. 26, 500 (1968)] gives an exact prediction of the mean elevation of the meniscus at any wall separation, whereas the classical LY equation for the elevation of the midpoint of the meniscus is accurate only when the separation approaches zero or infinity. When both walls are identical, the meniscus is symmetric about the midpoint, and the midpoint elevation is a more traditional and convenient measure of capillary rise than the mean elevation. Therefore, for this symmetric system a different equation is fitted to numerical predictions of the midpoint elevation and is shown to give excellent agreement for contact angles between 15 degrees and 160 degrees and wall separations up to 30 mm. When the walls have dissimilar surface properties, the meniscus generally assumes an asymmetric shape, and significant elevation of the liquid column can occur even when one of the walls has a contact angle significantly greater than 90 degrees. The height of the capillary rise depends on the spacing between the walls and also on the difference in contact angles at the two surfaces. When the contact angle at one wall is greater than 90 degrees but the contact angle at the other wall is less than 90 degrees, the meniscus can have an inflection point separating a region of positive curvature from a region of negative curvature, the inflection point being pinned at zero height. However, this condition arises only when the spacing between the walls exceeds a threshold value that depends on the difference in contact angles.