High-Pressure Synthesis of Bulk Cobalt Cementite, Co3C

Transition metal carbides find use in a wide range of advanced high-resilience applications including high-strength steels, heat shields, and deep-earth drills. However, carbides of the mid-to-late transition metals remain difficult to isolate and characterize on account of their metastability, which precludes the preparation of high-quality bulk single crystal samples using traditional solid-state methods. Herein, we report a combined computational and experimental survey of the cobalt--carbon binary system under high pressures, and demonstrate that pressure offers a route toward the bulk synthesis of the metastable cementite-type cobalt carbide, Co₃C, which under ambient conditions can only been prepared in low-dimensional thin film or nanoparticle form. First-principles calculations reveal two competitive low-energy stoichiometric phases under ambient pressures–Pnnm-Co₂C (Fe₂C-type) and Pnma-Co₃C (Fe₃C-type)—consistent with the known low-dimensional phases that have been studied for their promising magnetic properties. However, the calculated formation enthalpy of Pnma-Co₃C decreases steadily with applied pressure, while that of Pnnm-Co₂C increases. We pursue these results using high-pressure laser-heated synthesis methods coupled with in situ X-ray diffraction and observe the formation of Pnma-Co₃C above 4.8 GPa. We determine the experimental bulk modulus of Co₃C to be K₀ = 237 GPa (K_p = 4.0). First-principles calculations of the phonon modes in Co₃C reveal dynamical instabilities at ambient pressure that are absent under compression. These results offer a promising new route for the synthesis of rare-earth-free magnets.