ABSTRACT
Previous papers in this series have involved the study of water/ice in a sample of a mesoporous SBA-15 silica with a pore size of 86 Å, filling-factors f of 1.15 and 0.95. The present paper extends the study to partially filled samples with f = 0.6 and 0.4. It is found that the ice formed in the pores has characteristics that differ markedly from those seen in the previous measurements. For f = 0.6, there is a significant amount of hexagonal ice, as seen by the presence of the normal ice triplet. For f = 0.4, the triplet peaks are not seen, indicating the predominant formation of cubic ice superimposed on a broad diffuse scattering peak that is attributed to a defective form of low-density amorphous ice. A parameter-fitting routine has been used (as previously) to extract the variation of the peak intensities and shapes with temperature. A separate component analysis procedure confirms these conclusions and emphasizes the role of plastic ice in the phase conversion process for the 260-200 K temperature region. A comparison of the liquid phase data for filling-factors of 0.4 and 0.95 indicates that the structural characteristics of the water vary according to the thickness of the layer, as suggested by computer predictions.
Subject(s)
Ice , Silicon Dioxide/chemistry , Porosity , TemperatureABSTRACT
Neutron diffraction measurements for D(2)O in SBA-15 silica of pore diameter 86 Å have been made in a temperature range from 300 to 100 K. The pore-filling factor for the liquid phase is 0.95, resulting in an 'almost-filled' sample. The nucleation and transformation of the ice phase were determined for cooling and warming cycles at two different rates. The primary nucleation event at 258 K leads to a defective form of ice-I with predominantly cubic ice features. For temperatures below the main nucleation event, the data indicate the formation of an interfacial layer of disordered water/ice that varies with temperature and is reversible. The main diffraction peak for the water phase shows similar features to those observed in earlier studies, indicating enhanced hydrogen bonding and network correlations for the confined phase as the temperature is decreased. A detailed profile analysis of the triplet peak is presented in the accompanying paper (Seyed-Yazdi et al 2008 J. Phys.: Condens. Matter 20 205108).
ABSTRACT
The diffraction results for the formation of ice in 86 Å diameter pores of a SBA-15 silica sample are analysed to provide information on the characteristics of the ice created in the pores. The asymmetric triplet at â¼1.7 Å(-1), which involves several overlapping peaks, is particularly relevant to the different ice phases and contains a number of components that can be individually identified. The use of a set of three peaks with an asymmetric profile to represent the possibility of facetted growth in the pores was found to give an unsatisfactory fit to the data. The alternative method involving the introduction of additional peaks with a normal symmetric profile was found to give excellent fits with five components and was the preferred analytic procedure. Three peaks could be directly linked to the positions for the triplet of hexagonal ice, I(h), and one of the other two broad peaks could be associated with a form of amorphous ice. The variation of the peak intensity (and position) was systematic with temperature for both cooling and heating runs. The results indicate that a disordered state of ice is formed as a component with the defective crystalline ices. The position of a broad diffraction peak is intermediate between that of high-density and low-density amorphous ice. The remaining component peak is less broad but does not relate directly to any of the known ice phases and cannot be assigned to any specific structural feature at the present time.
