Phase transitions in disordered mesoporous solids.

Fluids confined in mesoporous solids exhibit a wide range of physical behavior including rich phase equilibria. While a notable progress in their understanding has been achieved for fluids in materials with geometrically ordered pore systems, mesoporous solids with complex pore geometries still remain a topic of active research. In this work we study phase transitions occurring in statistically disordered linear chains of pores with different pore sizes. By considering, quite generally, two phase change mechanisms, nucleation and phase growth, occurring simultaneously we obtain the boundary transitions and the scanning curves resulting upon reversing the sign of the evolution of the chemical potential at different points along the main transition branches. The results obtained are found to reproduces the key experimental observations, including the emergence of hysteresis and the scanning behavior. By deriving the serial pore model isotherm we suggest a robust framework for reliable structural analysis of disordered mesoporous solids.

Scale-dependent diffusion anisotropy in nanoporous silicon.

Nanoporous silicon produced by electrochemical etching of highly B-doped p-type silicon wafers can be prepared with tubular pores imbedded in a silicon matrix. Such materials have found many technological applications and provide a useful model system for studying phase transitions under confinement. This paper reports a joint experimental and simulation study of diffusion in such materials, covering displacements from molecular dimensions up to tens of micrometers with carefully selected probe molecules. In addition to mass transfer through the channels, diffusion (at much smaller rates) is also found to occur in directions perpendicular to the channels, thus providing clear evidence of connectivity. With increasing displacements, propagation in both axial and transversal directions is progressively retarded, suggesting a scale-dependent, hierarchical distribution of transport resistances ("constrictions" in the channels) and of shortcuts (connecting "bridges") between adjacent channels. The experimental evidence from these studies is confirmed by molecular dynamics (MD) simulation in the range of atomistic displacements and rationalized with a simple model of statistically distributed "constrictions" and "bridges" for displacements in the micrometer range via dynamic Monte Carlo (DMC) simulation. Both ranges are demonstrated to be mutually transferrable by DMC simulations based on the pore space topology determined by electron tomography.