Freezing and melting transitions of liquids in mesopores with ink-bottle geometry

Freezing and melting behavior of nitrobenzene in mesoporous silicon with different pore size and with different porous structure have been studied using H-1 NMR cryoporometry. With the bulk phase surrounding the porous monoliths, in materials with uniform channel-like pores distinct pore-size-dependent freezing and melting transitions have been measured. These data were further used for the analysis of the fluid behavior in samples with modulated porous structure, namely linear pores with alternating cross-section. We have, in particular, considered two materials consisting of channel sections, which were separated by almost identical channel `necks' but notably differed in the respective channel diameters. In the smaller channel segments, the observed shift in the freezing temperature provides direct evidence of the relevance of a pore-blocking mechanism, i.e. of the retardation in the propagation of a solid front by the channel necks. In the channel segments with larger diameter, on the other hand, freezing is found to be initiated by homogeneous nucleation.