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Phase relations in the B-BN system have been studied ex situ and in situ atpressures 2-20 GPa and temperatures up to 2800 K. The evolution of topology ofthe B-BN phase diagram has been investigated up to 24 GPa using models ofphenomenological thermodynamics with interaction parameters derived from ourexperimental data on phase equilibria at high pressures and high temperatures.There are two thermodynamically stable boron subnitrides in the system i.e.B13N2 and B50N2. Above 16.5 GPa the B50N2 = L + B13N2 peritectic reactiontransforms to the solid-phase reaction of B50N2 decomposition into tetragonalboron (t'-B52) and B13N2, while the incongruent type of B13N2 melting changesto the congruent type only above 23.5 GPa. The constructed phase diagramprovides fundamentals for directed high-pressure synthesis of superhard phasesin the B-BN system.

Phase diagram of the B-BN system at pressures up to 24 GPa: Experimental study and thermodynamic analysis