Mutual solubilities in crystalline phases in the system SiO2–GeO2 have been investigated up to 10 GPa pressure and 1500°C temperature, using a bulk composition of 50 mol% GeO2. Solid solution of up to 40 mol% GeO2 into the mineral quartz has been confirmed as well as solubility of Si into GeO2 rutile (argutite) and Ge into SiO2 rutile (stishovite) phases and limited Ge into coesite. Solubility of Ge in quartz is very high, and decreases with pressure, with the univariant quartz‐out reaction occurring near 3.4 GPa at 1200°C. The solubility of GeO2 in coesite is highest at 3.4 GPa (about 8 mol%) and decreases with increasing pressure. Significantly more extensive solubility than previously reported for the rutile phases has been found and measured in detail as a function of pressure and temperature. Extensive solubility of SiO2 in GeO2 is found in argutite at 1200°C, increasing strongly with pressure and reaching a maximum of 25.2 mol% SiO2 in GeO2 at 9 GPa. At this point coesite (ss) plus argutite (ss) react to form a stishovite phase with 18 mol% GeO2, and the mutual solubility in both phases decreases above this pressure. At 1500°C, similar solubilities are observed but the maximum SiO2 solubility in argutite of just over 25 mol% occurs near 10 GPa. All these solid solutions can be recovered to ambient temperature and pressure. Phase diagrams and unit cell information of the phases are presented here. Based on these results, a useful and industrially relevant, application for accurately measuring high pressure is suggested.
In the synthesis of the disordered lyotropic liquid crystalline L3 sponge phase prepared with the cosurfactants cetylpyridinium chloride and hexanol, aqueous NaCl solution is used as the solvent. When this sponge phase is used as the template for L3 silica-phase processing, we replace NaCl with HCl to facilitate the acid catalysis of tetramethoxysilane in forming a templated silica gel, assuming that changing the solvent from NaCl(aq) to HCl(aq) of equivalent ionic strength does not affect the stability range of the L3 phase. In this work, we confirm that changing the pH of the solvent from neutral to acidic (with HCl) has negligible effect on the L3 phase region. Equivalent ionic strength is provided by either NaCl(aq) or HCl(aq) solvent; therefore, a similar phase behavior is observed regardless of which aqueous solvent is used.
For a wide range of technological applications the need for optically transparent, monolithic, mesoporous silicates is readily apparent. Potential areas of utility include filtration, catalysis, and optoelectronics among many others. This laboratory has previously reported on the synthesis of such materials thatare formed through the addition of tetramethoxysilane to a liquid crystal solution of hexanol, cetylpyridinium chloride, and 0.2 M hydrochloric acid, and our investigation into the properties of these materials is a continuing process. We have achieved defect and fracture free material of suitable size (0.5 cm × 3 cm diameter disks) via supercritical drying of the silicate under ethanol or CO2. The dried materials are remarkably similar to ordinary glass in strength, texture, and clarity. They possess pore volumes of ca. 1.0 cm3/g, with BET surface areas >1000 m2/g. We can re-infiltrate thedried monolith with hydroxyethylacrylate, a photo-polymerizable monomer, to create an inorganic/organic nanocomposite. There is fracturing upon re-infiltration, but preliminary tests show that the polymerization proceeds despite the mechanical failure. These findings suggest many possible applications for these unique nanocomposites.
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