Energetics of high surface area silicas

The energetics and structure of high surface area, amorphous silicas prepared by low pressure chemical vapor deposition (LPCVD), flame hydrolysis and sol-gel were studied by high temperature transposed temperature drop calorimetry and solution calorimetry. Utilizing appropriate thermodynamic cycles, the total stored energy (measured as 'fast' energy release during drop experiments and as 'slow' energy release during solution experiments) of impurity free amorphous silicas relative to fused silica glass was determined. The 'fast' energy release involves the healing of point defects, reduction of surface area, release of strain, rearrangement of 2- and 3-fold rings by pore collapse or annealing of 2-fold rings (in conjunction with an appropriate concentration of 3- and 4-fold rings). The 'slow' energy release differences in the distribution of 3-fold and higher rings in annealed silica relative to fused silica glass. LPCVD film silicas had been deposited at 0.4 Torr pressure by the reaction of SiH₄ and excess O₂ and 523, 643 and 703 K. The total stored energy of 22 to 44 kJ/mol is mainly due to the presence of 2- and 3-fold rings, consistent with Raman and infrared spectra of films and diffraction studies on related 'snows'. The metastability of the LPCVD films decreases with increasing temperature of deposition due to the increased capacity to anneal metastable siloxane bonds. This trend continues to higher temperatures. An amorphous silica prepared by flame hydrolysis at 1073 K by the combustion of SiCl₄ in O₂ shows little or no stored energy and is energetically almost identical to fused silica glass. Acid- (pH ∼ 1) and base- (pH ∼ 11) catalyzed dry silica gels were prepared by mixing TEOS : ethanol: water in molar proportion 1 : 4 : 4, then aged at 333 K for 24 h and dried at 423 K for 2-3 days. 'Fast' energy release accounts for most of the total stored energy of 7.3 kJ/mol for acid-catalyzed and 66.2 kJ/mol for base-catalyzed dry silica gel. It is unlikely that high concentrations of 2- and 3-fold rings percontact with the aqueous medium during the sol-gel process. Therefore, the total stored energy arises predominantly from structural relaxation and rearrangement in the base-catalyzed gel and rearrangement of surface siloxane by pore collapse during volatile loss in the acid-catalyzed gel. The creation of metastable siloxanes from the rapid condensation of monomers (present due to the high solubility of silica in the basic solution) during the drying of the base-catalyzed gel may be the source of its extremely large metastability.