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High-surface-area silicon oxycarbide gels and glasses were synthesized from mixtures of methyldimethoxysilane (MDMS) and tetraethoxysilane (TEOS) through acidic hydrolysis and condensation. A surface area of ∼275 m2/g and an average pore size of ∼30 A was obtained for a 50% MDMS-50% TEOS glass at 800°C under a flowing argon atmosphere. The average pore size was increased by aging the precursor gels in ammonium hydroxide. The increased average pore size and the higher strength of the mesoporous gel network enhanced the surface-area stability of the glasses; in this case, surface areas >200 m2/g were retained at 1200°C under an argon atmosphere. 29Si MAS NMR spectra revealed that an oxycarbide structure was established in the mesoporous glasses obtained after pyrolysis of the aged gels. The role of carbon was demonstrated by comparing the surface-area stability of the oxycarbide glasses with that of pure silica and that of oxycarbide glasses where all the carbon groups were removed through low-temperature plasma-oxidation treatments. In the absence of carbon, the thermal stability of the surface area decreased dramatically.

The first attempts to introduce carbon into glass date back to 1951. But up until recently, the use of carbon or carbide raw materials, and the oxidation, volatilization and decomposition that accompany high temperature melting, have limited the synthesis of true silicon oxycarbide glasses. Here, the term silicon-oxycarbide refers specifically to a carbon-containing silicate glass wherein oxygen and carbon atoms share bonds with silicon in the amorphous, network structure. Thus, there is a distinction between black glass, which contains only a second-phase dispersion of elemental carbon, and oxycarbide glasses which usually contain both network carbon and elemental carbon. In addition to exploring the unique properties and applications of these glasses, per se, they are also of interest for developing models of the residual amorphous phases in polymer-derived silicon-carbide and silicon-nitride ceramics. The application of sol/gel techniques to glass synthesis has significantly advanced the development and characterization of silicon oxycarbide glasses. In this approach, alkyl-substituted silicon alkoxides, which are molecular precursors containing oxygen and carbon functionalities on the silicon, can be hydrolyzed and condensed without decomposition or loss of the carbon functional group. A low-temperature (

In this study, the surface chemistry and structure of methyl-substituted silica gels and porous oxycarbide glasses were investigated. FTIR was used to measure the relative concentration of Si−CH3 and Si−OH as a function of the degree of methyl-substitution and the pyrolysis temperature. The gels and glasses were further heated, dehydrated or hydrated, in situ, within the FTIR spectrometer. In the temperature range of 800–850°C, high surface area oxycarbide glasses were created with no detectable surface hydroxyl groups. Oxycarbide glasses synthesized in argon at 700°C displayed a weak band for surface hydroxyl groups and reversible physisorption of water, while those synthesized at 850/900°C showed a complete absence of surface hydroxyl groups and the formation of vicinal silanols upon chemisorption of water. Isolated silanols were observed upon heat treatment in vacuum. Formation of aromatic carbon species was found to correlate with the decomposition of the methyl groups. The oxycarbide surface is quite stable to densification (presumably due to elemental carbon on the pore surfaces). In the absence of oxygen, porous silicon oxycarbide glass powders maintain surface areas >200 m2/g at 1200°C. However, oxidizing species in the atmosphere deplete the aromatic carbon species, and the glasses lose surface area.