Chemical Stability and Thermal Equation of State of Si₃N₄: Implications for Nitrogen Storage in the Deep Earth

Abstract

Most nitrogen is predicted to reside in the Earth’s interior and could be in the form of nitrides. In this study, the chemical reaction of Si₃N₄ with SiO₂ was explored up to 50 GPa and 2 600 K using laser-heated diamond anvil cells combined with synchrotron radiation X-ray diffraction. The experimental results demonstrate that Si₃N₄ does not react with SiO₂ and cubic γ-Si₃N₄ remains stable at extreme pressure and temperature. First-principles calculations were performed to investigate the chemical stability of Si₃N₄ with the SiO₂-MgO assemblage, showing that Si₃N₄ can coexist with Mg₂SiO₄ and MgSiO₃ polymorphs. Based on our thermal equation of state of cubic γ-Si₃N₄, we suggest that cubic γ-Si₃N₄ is denser than the upper mantle but less dense than the lower mantle. The formation of Si₃N₄ in the early Earth may contribute to the nitrogen preservation in the deep mantle soon after crystallization of the mantle and Si₃N₄ is likely a precursor of nitrogen hosts in the modern deep Earth.

Keywords

nitrogen storage / Si₃N₄ / nitrides / high pressure and temperatures / X-ray diffraction / equation of state

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