Probing pore connectivity in random porous materials by scanning freezing and melting experiments

Freezing and melting behavior of nitrobenzene confined to pores of Vycor porous glass with random pore structure has been studied by means of nuclear magnetic resonance cryoporometry. The two transitions are found to reveal a broad hysteresis. To get deeper insight into the mechanisms leading to this phenomenon, scanning experiments exploiting temperature reversal upon incomplete freezing or melting have been performed. In this way, it was found that different cooling and warming histories result in different solid-liquid configurations within the pore system. Further evolution of the thus-attained configurations with changing temperature unveiled important information about the transition paths. In particular, these experiments indicated the occurrence of a pronounced pore blocking for freezing, resulting in freezing transitions via invasion percolation. The melting, on the other hand, is found to occur homogeneously over the whole pore network.