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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 ${\mathsf{\gamma }}^{\prime }\to \mathsf{\alpha }+{\mathsf{\epsilon }}^{\prime }$ 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 ${\mathsf{\gamma }}^{\prime }\rightleftharpoons {\mathsf{\epsilon }}^{\prime }$ are discussed. Full article

The Boqueirão granitic pegmatite, alias Alto da Cabeça pegmatite, is situated in Borborema Pegmatitic Province (BPP) in Northeast Brazil. This pegmatitic province hosts globally important reserves of tantalum and beryllium, as well as significant quantities of gemstones, including aquamarine, morganite, and the high-quality turquoise-blue “Paraíba Elbaite”. The studied lithium-cesium-tantalum Boqueirão granitic pegmatite intruded meta-conglomerates of the Equador Formation during the late Cambrian (502.1 ± 5.8 Ma; ⁴⁰Ar/³⁹Ar plateau age of muscovite). The pegmatite exhibits a typical zonal mineral pattern with four defined zones (Zone I: muscovite, tourmaline, albite, and quartz; Zone II: K-feldspar (microcline), quartz, and albite; Zone III: perthite crystals (blocky feldspar zone); Zone IV: massive quartz). Huge individual beryl, spodumene, tantalite, and cassiterite crystals are common as well. Microscopic examinations revealed that melt inclusions were entrapped simultaneously with fluid inclusions, suggesting the magmatic–hydrothermal transition. The magmatic–hydrothermal transition affected the evolution of the pegmatite, segregating volatile compounds (H₂O, CO₂, N₂) and elements that preferentially partition into a fluid phase from the viscous silicate melt. Fluid inclusion studies on microcline and associated quartz combined with microthermometry and Raman spectroscopy gave an insight into the P-T-X characteristics of entrapped fluids. The presence of spodumene without other LiAl(SiO₃)₂ polymorphs and constructed fluid inclusion isochores limited the magmatic–hydrothermal transition at the gem-bearing Boqueirão granitic pegmatite to the temperature range between 300 and 415 °C at a pressure from 1.8 to 3 kbar. Full article