Dispersion transition and the nonergodicity of the disordered nanoporous medium-nonwetting liquid system

Abstract

The experiments in which a nonwetting liquid does not flow from a disordered nanoporous medium are described. The outflow is shown to depend on the degree of filling of the porous medium and its temperature in a critical manner. A physical mechanism is proposed where the transition of a system of liquid nanoclusters in a confinement into a metastable state in narrow filling and temperature ranges results from the appearance of a potential barrier due to the fluctuations of the collective “multiparticle” interaction of liquid nanoclusters in neighboring pores of different sizes at the shell of a percolation cluster of filled pores. The energy of a metastable state forms a potential relief with numerous maxima and minima in the space of a porous medium. The dispersed liquid volume in a metastable state is calculated with an analytical percolation theory for a ground state with an infinite percolation cluster. The outflow time distribution function of pores is calculated, and a power law is obtained for the decrease in nonwetting liquid volume retained in a porous medium with increasing time. The relaxation of the system under study is a multistage process accompanied by discontinuous equilibrium and overcoming of numerous local maxima of a potential relief. The formation of the metastable state of retained nonwetting liquid results from the nonergodicity properties of a disordered porous medium. The proposed model can describe the detected dependences of dispersed liquid volume on the degree of filling and temperature.