Low temperature heat capacity measurements of β-Si3N4 and γ-Si3N4: Determination of the equilibrium phase boundary between β-Si3N4 and γ-Si3N4

Isobaric heat capacities of β-Si₃N₄ and γ-Si₃N₄ were measured at temperatures between 1.8 and 309.9 K with a thermal relaxation method. The measured heat capacities of γ-Si₃N₄ are smaller than those of β-Si₃N₄ in this temperature range. Using these data, we determined the standard entropies of β-Si₃N₄ and γ-Si₃N₄ to be 62.30 J·mol^?1 K^?1 and 51.79 J·mol^?1 K^?1, respectively. The equilibrium phase boundary between β-Si₃N₄ and γ-Si₃N₄ was calculated using these values and thermodynamic parameters reported in previous studies. The obtained equilibrium phase transition pressure at 2000 K is 11.4 GPa. It is lower than the experimental pressures at which γ-Si₃N₄ was synthesized in previous studies. The calculated Clapeyron slope at this temperature is 0.6 MPa K^?1, which is consistent with those of theoretical studies.