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High-Pressure Chemistry of Carbon Nitride Materials

Published online by Cambridge University Press:  10 February 2011

Andrew J. Stevens ,
Carl B. Agee  and
Charles M. Lieber
Andrew J. Stevens
Affiliation:
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138
Carl B. Agee
Affiliation:
Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138
Charles M. Lieber
Affiliation:
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138
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Abstract

The composition and properties of the sp2-bonded carbon nitride precursor paracyanogen (pCN) has been studied at high pressures and temperatures. Paracyanogen decomposes to carbon and molecular nitrogen with the decomposition temperature increasing with pressure over the range of 3 to 19 GPa. Prior to decomposition, pCN can be transformed to an atmospheric-pressure quenchable phase that is more than 25% higher in density and over an order of magnitude harder than the starting material. Structural analysis of this quenchable phase shows, however, that it consists of a sp2-bonded network. In addition, the decomposition kinetics of paracyanogen have been studied in detail. Rapid, self-propagating decomposition occurs above a threshold temperature. Below this, decomposition rates exhibit an Arrhenius behavior with activation energy and volume of 2.7 eV and 3.9 Å3, respectively The decomposition rates depend on the nitrogen density and decrease significantly with lower nitrogen concentration. Kinetic effects favoring a graphite-like, sp2-bonded structure may preclude the high-pressure synthesis of superhard, sp3-bonded carbon nitride solids below their thermodynamic stability limit, unless an optimally designed precursor is employed.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 499: Symposium DD – High Pressure Materials Research , 1997 , 309
Copyright
Copyright © Materials Research Society 1998

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References

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