Prediction of orientational phase transition in boron carbide

The assessed binary phase diagram of boron–carbon exhibits a single intrinsically disordered alloy phase designated “B4C” with rhombohedral symmetry occupying a broad composition range that falls just short of the nominal carbon content of 20%. As this composition range is nearly temperature independent, the phase diagram suggests a violation of the third law of thermodynamics, which typically requires compounds to achieve a definite stoichiometry at low temperatures. By means of first principles total energy calculations we predict the existence of two stoichiometric phases at T = 0 K: one of composition B4C with monoclinic symmetry; the other of composition B13C2 with rhombohedral symmetry. Using statistical mechanics to extend to finite temperatures, we demonstrate that the monoclinic phase reverts to the observed disordered nonstoichiometric rhombohedral phase above T = 600 K, along with a slight reduction on carbon content.