Cavitation in metastable fluids confined to linear mesopores

We study the adsorption process of nitrogen (at 77.4 and 51.3 K) and argon (at 60 K) in porous silicon duplex layers, Si/A/B and Si/B/A, where the pores of A are on average narrower than the pores of B. We compare the experimental isotherms to that calculated from elemental isotherms measured in layers A and B supported by or detached from the silicon substrate. This allows us to confirm our previous studies which show that the relaxation of the substrate constraint modifies the adsorption strains and leads to a decrease of the adsorbed amount before condensation and consequently increases the condensation pressure. In the so-called ink-bottle Si/B/A configuration, layer B empties while layer A remains filled which proves that layer B empties via cavitation. The vapor pressure at which cavitation occurs in layer B in Si/B/A configuration is close to the pressure at which the same layer empties when it is in direct contact with the gas reservoir (Si/A/B configuration) which indicates that layer B contains all the ingredients necessary for cavitation to occur. The absolute value of the liquid pressure at which cavitation occurs is much lower than the value predicted by the theory of homogeneous nucleation. Nucleation of gas bubbles thus takes place on the surface of the pore walls. This is the crucial point of the paper. A receding meniscus with a contact angle lower than π/2 inside a pore and a gas bubble with a contact angle higher than π/2 are thus mutually exclusive. A receding meniscus cannot enter a pore. This has nothing to do with a pore-blocking effect; this is related to the physical parameters which define the contact angle inside the pores, that is, the surface energies at the solid-liquid, solid-vapor, and liquid-vapor interfaces. For argon at 60 K in the Si/B/A duplex layer, cavitation in layer B activates the emptying of a fraction of pores of layer A which constitutes a direct observation of metastable states.