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Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

ABSTRACT: Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content and stability at ambient conditions are mutually exclusive, thereby making the synthesis of such materials challenging. One way to stabilize such compounds is the application of high pressure. Here, through a direct reaction between Fe and N₂ in a laser-heated diamond anvil cell, we synthesize three ironnitrogen compounds Fe₃N₂, FeN₂ and FeN₄. Their crystal structures are revealed by single-crystal synchrotron X-ray diffraction. Fe₃N₂, synthesized at 50?GPa, is isostructural to chromium carbide Cr₃C₂. FeN₂ has a marcasite structure type and features covalently bonded dinitrogen units in its crystal structure. FeN₄, synthesized at 106?GPa, features polymeric nitrogen chains of [N₄^2-]_n units. Based on results of structural studies and theoretical analysis, [N₄^2-]_n units in this compound reveal catena-poly[tetraz-1-ene-1,4-diyl] anions.

SUBMITTER: Bykov M

PROVIDER: S-EPMC6048061 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

Bykov M M Bykova E E Aprilis G G Glazyrin K K Koemets E E Chuvashova I I Kupenko I I McCammon C C Mezouar M M Prakapenka V V Liermann H-P HP Tasnádi F F Ponomareva A V AV Abrikosov I A IA Dubrovinskaia N N Dubrovinsky L L

Nature communications 20180716 1

Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content and stability at ambient conditions are mutually exclusive, thereby making the synthesis of such materials challenging. One way to stabilize such compounds is the application of high pressure. Here, through a direct reaction between Fe and N<sub>2</sub> in a laser-heated diamond anvil cell, we synthesize ...[more]

PMID: 30013071

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Project description: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.

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Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

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Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

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