Anomalously slow relaxation of a nonwetting liquid in the disordered confinement of a nanoporous medium

The time evolution of the water–disordered nanoporous medium Libersorb 23 (L23) system has been studied after complete filling at elevated pressure followed by full release of overpressure. It is established that relaxation of the L23 rapidly flows out during the overpressure relief time, following the variation in pressure. At a temperature below that of the dispersion transition (T < T _d = 284 K), e.g., at T = 277 K, the degree of filling θ decreases from 1 to 0.8 within 10 s. The degree of filling varies with time according to the power law θ ~ t ^–α with the exponent α < 0.1 over a period of t ~ 10⁵ s. This process corresponds to slow relaxation of a metastable state of a nonwetting liquid in a porous medium. At times t > 10⁵ s, the metastable state exhibits decay, manifested as the transition to a power dependence of θ(t) with a larger exponent. The relaxation of the metastable state of nonwetting liquid in a disordered porous medium is described in the mean field approximation as a continuous sequence of metastable states with a barrier decreasing upon a decrease in the degree of filling. Using this approach, it is possible to qualitatively explain the observed relaxation process and crossover transition to the stage described by θ(t) with a larger exponent.