Phase Stability of Iron Nitride Fe4N at High Pressure—PressureDependent Evolution of Phase Equilibria in the Fe–N System

0543946 - ÚFM 2022 RIV CH eng J - Článek v odborném periodiku
Wetzel, M. H. - Rabending, T. T. - Friák, Martin - Všianská, Monika - Šob, Mojmír - Leineweber, A.
Phase Stability of Iron Nitride Fe4N at High Pressure—PressureDependent Evolution of Phase Equilibria in the Fe–N System.
Materials. Roč. 14, č. 14 (2021), č. článku 3963. E-ISSN 1996-1944
Institucionální podpora: RVO:68081723
Klíčová slova: iron nitride * high pressure * phase stability * phase transitions * phase diagrams
Obor OECD: Condensed matter physics (including formerly solid state physics, supercond.)
Impakt faktor: 3.748, rok: 2021
Způsob publikování: Open access
https://www.mdpi.com/1996-1944/14/14/3963

Although the general instability of the iron nitride γ′-Fe4N with respect to other phases at high pressure is well established, the actual type of phase transitions and equilibrium conditions of their occurrence are, as of yet, poorly investigated. In the present study, samples of γ′-Fe4N and mixtures of α Fe and γ′-Fe4N powders have been heat-treated at temperatures between 250 and 1000 °C and pressures between 2 and 8 GPa in a multi-anvil press, in order to investigate phase equilibria involving the γ′ phase. Samples heat-treated at high-pressure conditions, were quenched, subsequently decompressed, and then analysed ex situ. Microstructure analysis is used to derive implications on the phase transformations during the heat treatments. Further, it is confirmed that the Fe–N phases in the target composition range are quenchable. Thus, phase proportions and chemical composition of the phases, determined from ex situ X-ray diffraction data, allowed conclusions about the phase equilibria at high-pressure conditions. Further, evidence for the low-temperature eutectoid decomposition γ′→α+ε′ is presented for the first time. From the observed equilibria, a P–T projection of the univariant equilibria in the Fe-rich portion of the Fe–N system is derived, which features a quadruple point at 5 GPa and 375 °C, above which γ′-Fe4N is thermodynamically unstable. The experimental work is supplemented by ab initio calculations in order to discuss the relative phase stability and energy landscape in the Fe–N system, from the ground state to conditions accessible in the multi-anvil experiments. It is concluded that γ′-Fe4N, which is unstable with respect to other phases at 0 K (at any pressure), has to be entropically stabilised in order to occur as stable phase in the system. In view of the frequently reported metastable retention of the γ′ phase during room temperature compression experiments, energetic and kinetic aspects of the polymorphic transition γ′⇌ε′ are discussed.
Trvalý link: http://hdl.handle.net/11104/0322635