Silicon Oxycarbide Glasses

Journal of Sol-Gel Science and Technology 14, 7–25 (1999) c 1999 Kluwer Academic Publishers. Manufactured in The Netherlands. °

Silicon Oxycarbide Glasses CARLO G. PANTANO, ANANT K. SINGH∗ AND HANXI ZHANG∗∗ Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802, USA Received August 4, 1998; Accepted October 22, 1998

Abstract. 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 secondphase 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 (1400◦ C) glasses also show amorphous and graphitic carbon species in the glasses, the Raman spectra of 800–1000◦ C glasses are featureless. Since the visual appearance of the glasses, and the 13 C NMR spectra, verify the presence of elemental carbon in the glasses, the absence of a Raman spectra reveals that the size of

the elemental carbon species is below a critical size. According to both Lespade et al. [57] and Knight and White [58], there exists a coherence length (L a ) that must be exceeded to create a Raman signal. In the case of amorphous and crystalline carbons, this coherence length is estimated to be ∼2.5 nm. Thus, one can conclude that the free carbon species in the 800– 1000◦ C glasses are dispersed in the glass at a scale 1200◦ C) of these glasses is limited, but it is quite likely that with further development of composition and processing, their controlled heattreatment could yield useful glass-ceramics containing silicon-carbide and graphite. The current level of activity and interest in these materials suggest that these advancements can be expected. Now, the primary challenge is to establish properties for these new and unique glasses, so that their practical applications can proceed. Acknowledgments The authors gratefully acknowledge the National Science Foundation (DMR-9118797) for their financial support. Thanks are also extended to Alan Benesi, Else Breval, James Hamilton, Paolo Colombo and Mike Hammond. References 1. C.J. Brinker and G.W. Scherer, Sol-Gel Science (Academic Press, San Diego, 1990). 2. H. Schmidt, Organic modification of the glass structure, J. NonCryst. Solids 112, 419–423 (1989). 3. R. Ellis, Method of making electrically conducting glass and articles made therefrom, U.S. Pat. 2,556,616, June 1951.

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