Abstract
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 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 are discussed.
Highlights
The large body of research devoted to the Fe–N system is mainly motivated by its high technological relevance in the field of surface treatment of iron and steel parts [1]
The exchange and correlation energy were treated within the generalised gradient approximation (GGA) as parametrised by Perdew, Burke, and Ernzerhof (PBE) [39]
According to the results presented so far, interpretation of the determined unit‐cell volumes using the reported lattice parameters a and c experiment of quenched data of the dual-phase γ + ε and single-phase ε samples were used to derive such a composition data in terms of phase equilibria attained at the high-pressure tr nitrides
Summary
The large body of research devoted to the Fe–N system is mainly motivated by its high technological relevance in the field of surface treatment of iron and steel parts [1]. Studies covering microstructure evolution and mechanical properties of nitrided surface layers predominate, there has been, and still exists, a growing interest in the fundamental 4.0/). This can be attributed to the peculiar magnetic properties of the iron nitrides contrasting the magnetism of the allotropes of pure. Fe. The Fe–N system offers a unique opportunity to study phase stability of the various allotropes of Fe (α-bcc, γ-fcc, and ε-hcp) being subject to modified stability by the presence of interstitial atoms. In contrast to the Fe–C system, the Fe–N system is ideal for such studies due to the existence of structural similarity between the terminal solid solutions and the interstitial compounds. The structures of Fe–N phases up to the composition of
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