Sen, S. and Widgeon, S. J. and Navrotsky, A. and Mera, G. and Tavakoli, A. and Ionescu, E. and Riedel, R. (2013):
Carbon substitution for oxygen in silicates in planetary interiors.
In: Proceedings of the National Academy of Sciences, 110 (40), pp. 15904-15907, ISSN 0027-8424,
[Online-Edition: http://dx.doi.org/10.1073/pnas.1312771110],
[Article]

Abstract

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiOxC4-x tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiOxC4-x tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10–100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle.

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