PENTACOORDINATE SILICON COMPLEXES AS PRECURSORS TO SILICATE-GLASSES AND CERAMICS

The recent discovery that pentacoordinate alkali glycolato silicates such as monomeric MSi(OCH2CH2O)2OCH2CH2OH or dimeric M2Si2(OCH2CH2O)5 (where M = Li, Na, K, or Cs) can be synthesized directly from SiO2, ethylene glycol, and MOH suggests that these compounds may serve as useful, inexpensive precursors to alkali silicate glasses or ceramics, either by sol-gel processing or by simple pyrolysis. We report here studies on the chemical changes and phase transformations that occur during the pyrolytic transformation of these compounds to ceramic and glassy materials. The evolutionary processes encountered as the materials are heated to selected temperatures were followed by X-ray powder diffraction, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and thermal analysis techniques. In general, the crystalline compounds oxidatively decompose at temperatures above 300-degrees-C to form amorphous materials. At higher temperatures, the line compounds M2Si2O5 begin to crystallize. During the transformation process, ligand oxidation forms CO2 and H2O which react with the alkali metals to form small amounts of carbonates as seen by DRIFTS. At higher temperatures, the carbonates decompose with coincident formation of the primary crystalline phase, except in the case of the potassium compound, which exhibits some phase segregation.