Capillary condensation as a morphological transition

The process of capillary condensation/ evaporation in cylindrical pores is considered within the idea of symmetry breaking. Capillary condensation/evaporation is treated as a morphological transition between the wetting film configurations of different symmetry. We considered two models: (i) the classical Laplace theory of capillarity and (ii) the Derjaguin model which takes into account the surface forces expressed in terms of the disjoining pressure. Following the idea of Everett and Haynes, the problem of condensation/ evaporation is considered as a transition from bumps/undulations to lenses. Using the method of phase portraits, we discuss the mathematical mechanisms of this transition hidden in the Laplace and Derjaguin equations. Analyzing the energetic barriers of the bump and lens formation, it is shown that the bump formation is a prerogative of capillary condensation: for the vapor-liquid transition in a pore, the bump plays the same role as the spherical nucleus in a bulk fluid. We show also that the Derjaguin model admits a variety of interfacial configurations responsible for film patterning at specific conditions. (C) 2002 Elsevier Science B.V. All rights reserved.