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Capillary forces are commonly encountered in nature because of the spontaneous condensation of liquid from surrounding vapor, leading to the formation of a liquid bridge. In most cases, the advent of capillary forces by condensation leads to undesirable events such as an increase in the strength of granules, which leads to flow problems and/or caking of powder samples. The prediction and control of the magnitude of capillary forces is necessary for eliminating or minimizing these undesirable events. The capillary force as a function of the separation distance, for a liquid bridge with a fixed volume in a sphere/plate geometry, was calculated using different expressions reported previously. These relationships were developed earlier, either on the basis of the total energy of two solid surfaces interacting through the liquid and the ambient vapor or by direct calculation of the force as a result of the differential gas pressure across the liquid bridge. It is shown that the results obtained using these methodologies (total energy or differential pressure) agree, confirming that a total-energy-based approach is applicable, despite the thermodynamic nonequilibrium conditions of a fixed volume bridge rupture process. On the basis of the formulas for the capillary force between a sphere and a plane surface, equations for the calculation of the capillary force between two spheres are derived in this study. Experimental measurements using an atomic force microscope (AFM) validate the formulas developed. The most common approach for transforming interaction force or energy from that of sphere/plate geometry to that of sphere/sphere geometry is the Derjaguin approximation. However, a comparison of the theoretical formulas derived in this study for the interaction of two spheres with those for sphere/plate geometry shows that the Derjaguin approximation is only valid at zero separation distance. This study attempts to explain the inapplicability of the Derjaguin approximation at larger separation distances. In particular, the area of a liquid bridge changes with the separation distance, H, and thereby does not permit the application of the "integral method," as used in the Derjaguin approximation.

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