Neutron diffraction and NMR relaxation studies of structural variation and phase transformations for water/ice in SBA-15 silica: I. The over-filled case

Neutron diffraction and NMR relaxation measurements have been made of water/ice in SBA-15, a mesoporous silica constituting an ordered array of cylindrical mesopores of pore diameter similar to 86 angstrom, over the temperature range 180-300 K in a cooling and heating cycle. The over-filled sample shows the initial formation of hexagonal ice on the outside of the silica grains, followed by the nucleation of cubic ice inside the pores at a lower temperature. Neutron scattering profiles for the cubic ice peaks are significantly broadened and indicate a defective structure, as observed in previous experiments on ice formation in sol-gel and MCM-type silicas. Below the pore freezing temperature the intensity of the cubic ice peaks exhibit a significant increase, down to the lowest experimental temperature, indicating a reversible conversion of defective ice to ordered ice crystals. The peak profile analysis for the two ice patterns indicates a systematic variation in the position as a function of temperature, giving values of the expansion coefficients that are slightly lower than other measurements for the bulk phase. NMR results on proton relaxation as a function of temperature indicate the presence of a mobile phase for temperatures below pore freezing that supports the view that there is interconversion between brittle and plastic phases of ice.