Crystallization of Polymer‐Derived Silicon Carbonitride at 1873 K under Nitrogen Overpressure

The chemical stability of an amorphous silicon carbonitride ceramic, having the composition 0.57SiC·0.43Si 3 N 4 ·0.49C is studied as a function of nitrogen overpressure at 1873 K. The ceramic suffers a weight loss at p N2 < 3.5 bar (1 bar = 100 kPa), does not show a weight change from 3.5 to 11 bar, and gains weight above 11 bar. The structure of the ceramic changes with pressure: it is crystalline from 1 to 6 bar, amorphous at ∼10 bar, and is crystalline above ∼10 bar. The weight‐loss transition, at 3.5 bar, is in excellent agreement with the prediction from thermodynamic analysis when the activities of carbon, SiC, and Si 3 N 4 are set equal to those of the crystalline forms; this implies that the material crystallizes before decomposition. The amorphous to crystalline transition that occurs at ∼10 bar, and which is accompanied by weight gain, is likely to have taken place by a different mechanism. A nucleation and growth reaction with the atmospheric nitrogen is proposed as the likely mechanism. The supersaturation required to nucleate α‐Si 3 N 4 crystals is calculated to be 30 kJ/mol.