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Abstract: The general equation is derived for the equilibrium of a small solid particle and a large solution, being consistent with the thermodynamics of Gibbs. This equation can be solved in a closed form for solubility if an ideal (or an infinitely diluted) solution is considered, if the interfacial energy is independent of the composition of the solution and if all physical parameters (other than the solubility itself) are taken size independent. The solubility of the particles is found to increase with increasing its specific surface area, i.e. if non-spherical particles are applied. This simplified solution further simplifies if the shape of the solid is supposed to be spherical. This latter equation, however, is found to be in contradiction with the Ostwald–Freundlich equation, widely used in chemistry, biology and materials science to describe the size dependence of solubility of a spherical crystal. The reason for its incorrectness is shown to be due to the incorrect application of the Laplace equation. It is found that the solubility increases with decreasing the size of the dissolving phase not due to the increased curvature of the phase (Kelvin and Freundlich), but rather due to the increased specific surface area of the phase (Gibss, Ostwald). Equations are also derived for the case, when the size effect of the interfacial energy is taken into account, and when the crystal is surrounded by several planes of different interfacial energies. The role of wettability is discussed on the size dependence of solubility. [Copyright &y& Elsevier]

Abstract: Fourier transform absorption spectroscopy in the 500–6000cm−1 and 9–300K ranges is applied to monitor the effects produced by Eu3+ incorporation into sol–gel silica samples doped with concentration increasing from 0.001 to 10mol%. The aim is to investigate the formation of aggregates by exploiting the Eu3+ crystal-field transitions. Complementary microreflectance and Raman spectra are also measured in the range of silica intrinsic vibrational modes to confirm the hypothesis of matrix modification induced by increasing doping levels. Evidences of clustering are found for high Eu3+ concentrations. Up to 3mol% the crystal-field line intensities gradually increase and the OH− content smoothly decreases. A further increase to 10mol% causes drastic, remarkable changes, i.e. sharp crystal-field lines appear which narrow by lowering the temperature. Furthermore, the OH− related bands are no longer detectable. For concentrations up to 3mol% the aggregates are amorphous as the silica matrix, while for the Eu3+ 10mol% sample they show a rather ordered structure. [Copyright &y& Elsevier]

Transmission electron microscopy, Raman scattering, Fourier transform infrared spectroscopy, and radio-luminescence are employed to investigate rare-earth (RE) incorporation and aggregate formation in silica glasses prepared by the Sol-Gel method and doped with Ce3+, or Tb3+, Gd3+, Yb3+ with concentrations up to several mol%. The results demonstrate that rare-earth aggregates with a mean diameter extending up to several tens of nanometers occur, further increasing their size after post-densification high temperature treatments. Rare-earth segregation causes a reduction of the OH content of glasses. Nanoclusters are amorphous, possibly close to a (RE)2SiO5 stoichiometry. Room temperature radio-luminescence measurements reveal that the emission spectra are dominated by RE3+ emissions and no bands due to silica matrix defects are detected. [ABSTRACT FROM AUTHOR]