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  1. Abstract

    Although high pressure enables alloying between hydrogen and iron, hydrogen‐to‐iron molar ratio (H/Fe) so far found in experiments is mostly limited to 1 in the close‐packed iron metal under high pressure. We report a H/(Fe + Ni) ratio of 1.8 ± 0.1 from (Fe,Ni)Hx(orx ≥ 1.8) quenched from liquid, exceeding the amounts so far reported for densely packed Fe alloys. From the metastable behavior of the frozen (Fe,Ni)Hxliquid during decompression, we infer that the amount is a lower bound and therefore even a greater amount of H can be dissolved in the liquid part of Fe‐rich cores of planets. The significant H storage capacity of liquid Fe‐Ni alloy is important to consider for potential storage of H in the interiors of low‐density planets as well as rocky planets.

     
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  2. Abstract

    The occurrences and cycling of slab‐originated carbon and hydrogen are considered to be controlled by their reactions with metallic iron from mantle disproportionation and slab serpentinization, to form Fe alloys containing carbon and hydrogen. Here we show experimental results on the phase relations and melting of the Fe‐C‐H system using laser‐heated diamond anvil cell and X‐ray diffraction techniques up to 72 GPa. The incorporation of hydrogen was found to lower the eutectic melting temperatures of Fe‐C alloy by ∼50–178 K at 20–70 GPa, facilitating the formation of metallic liquids in the deep mantle and thus enhancing the mobility and deep cycling of subducted carbon and hydrogen. Hydrogen also substitutes with carbon in Fe‐C metal to form hydride and diamond at relatively high‐temperature conditions (e.g., 42.6 GPa, >1885 K and 71.8 GPa, >1798 K). The hydrogen‐carbon‐enriched metallic liquids provide the necessary fluid environment for superdeep diamond growth.

     
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  3. Abstract

    Iron‐dominant metallic phases are likely the primary hosts for nitrogen in the reduced deep Earth, hence the storage of nitrogen in the lower mantle and the core is governed by the behavior of the Fe‐N‐C system at high temperatures and pressures. In this study, phase transitions and thermoelastic properties of iron carbonitrides were investigated at high pressure‐temperature conditions by diamond anvil cell experiments and first‐principles calculations. Experimental data revealed no phase transition inε‐type Fe4(N0.6C0.4) or Fe7(N0.75C0.25)3up to 60 GPa at room temperature. At high temperature, Fe7(N0.75C0.25)3transforms into the Fe3C‐type phase at ∼27 GPa, and then into the Fe7C3‐type phase at ∼45 GPa, which is also corroborated by our theoretical calculations. We found that the phase stability of iron carbonitrides mainly depends on the N/C ratio, and the elastic properties of iron carbonitrides are dominantly affected by the Fe/(N+C) ratio. Iron carbonitrides with diverse structures may be the main host for nitrogen in the deep mantle. Some iron carbonitride inclusions in lower mantle diamonds could be the residue of the primordial mantle or originate from subducted nitrogen‐bearing materials, rather than iron‐enriched phases of the outer core. In addition, our experiments confirmed the existence of Fe7C3‐type Fe7C3‐Fe7N3solid solutions above 40 GPa. Fe7C3‐type Fe7(C, N)3has comparable density and thermoelastic properties to its isostructural endmembers and may be a promising candidate constituent of the Earth's inner core.

     
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  4. Abstract

    The presence of light elements in the metallic cores of the Earth, the Moon, and other rocky planetary bodies has been widely proposed. Carbon is among the top candidates in light of its high cosmic abundance, siderophile nature, and ubiquity in iron meteorites. It is, however, still controversial whether carbon‐rich core compositional models can account for the seismic velocity observations within the Earth and lunar cores. Here, we report the density and elasticity of Fe90Ni10‐3 wt.% C and Fe90Ni10‐5 wt.% C liquid alloys using synchrotron‐based X‐ray absorption experiments and first‐principles molecular dynamics simulations. Our results show that alloying of 3 wt.% and 5 wt.% C lowers the density of Fe90Ni10liquid by ∼2.9–3.1% at 2 GPa, and ∼3.4–3.6% at 9 GPa. More intriguingly, our experiments and simulations both demonstrate that the bulk moduli of the Fe‐Ni‐C liquids are similar to or slightly higher than those of Fe‐Ni liquids. Thus, the calculated compressional velocities (vp) of Fe‐Ni‐C liquids are higher than that of pure Fe‐Ni alloy, promoting carbon as a possible candidate to explain the elevatedvpin the Earth's outer core. However, the values and slopes of both density andvpof the studied two Fe‐Ni‐C liquids do not match the outer core seismic models, suggesting that carbon may not be the sole principal light element in Earth's outer core. The highvpof Fe‐Ni‐C liquids does not match the presumptivevpof the lunar outer core well, indicating that carbon is less likely to be its dominant light element.

     
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  5. Abstract

    Fe‐Al‐bearing bridgmanite may be the dominant host for ferric iron in Earth's lower mantle. Here we report the synthesis of (Mg0.5Fe3+0.5)(Al0.5Si0.5)O3bridgmanite (FA50) with the highest Fe3+‐Al3+coupled substitution known to date. X‐ray diffraction measurements showed that at ambient conditions, the FA50 adopted the LiNbO3structure. Upon compression at room temperature to 18 GPa, it transformed back into the bridgmanite structure, which remained stable up to 102 GPa and 2,600 K. Fitting Birch‐Murnaghan equation of state of FA50 bridgmanite yieldsV0 = 172.1(4) Å3,K0 = 229(4) GPa withK0′ = 4(fixed). The calculated bulk sound velocity of the FA50 bridgmanite is ~7.7% lower than MgSiO3bridgmanite, mainly because the presence of ferric iron increases the unit‐cell mass by 15.5%. This difference likely represents the upper limit of sound velocity anomaly introduced by Fe3+‐Al3+substitution. X‐ray emission and synchrotron Mössbauer spectroscopy measurements showed that after laser annealing, ~6% of Fe3+cations exchanged with Al3+and underwent the high‐ to low‐spin transition at 59 GPa. The low‐spin proportion of Fe3+increased gradually with pressure and reached 17–31% at 80 GPa. Since the cation exchange and spin transition in this Fe3+‐Al3+‐enriched bridgmanite do not cause resolvable unit‐cell volume reduction, and the increase of low‐spin Fe3+fraction with pressure occurs gradually, the spin transition would not produce a distinct seismic signature in the lower mantle. However, it may influence iron partitioning and isotopic fractionation, thus introducing chemical heterogeneity in the lower mantle.

     
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  6. Abstract Magnetic and electronic properties of quantum materials heavily rely on the crystal structure even in the same chemical compositions. In this study, it is demonstrated that a layered tetragonal EuCd 2 Sb 2 structure can be obtained by treating bulk trigonal EuCd 2 Sb 2 under high pressure (6 GPa) and high temperature (600 °C). Magnetization measurements of the newly formed layered tetragonal EuCd 2 Sb 2 confirm an antiferromagnetic ordering with Neel temperature ( T N ) around 16 K, which is significantly higher than that ( T N ≈ 7 K) of trigonal EuCd 2 Sb 2 , consistent with heat capacity measurements. Moreover, bad metal behavior is observed in the temperature dependence of the electrical resistivity and the resistivity shows a dramatic increase around the Neel temperature. Electronic structure calculations with local density approximation dynamic mean–field theory (LDA+DMFT) show that this material is strongly correlated with well‐formed large magnetic moments, due to Hund's coupling, which is known to dramatically suppress the Kondo scale. 
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    Free, publicly-accessible full text available July 1, 2024
  7. Nanocrystalline olivine-structured Mg2SiO4 and MgCoSiO4, with an average particle size of 27 nm and 31 nm, respectively, were successfully synthesized from oxide precursors via mechanochemical methods. The two nanocrystalline products were obtained after milling for 360 min and displayed high concentrations of Mg2SiO4 (>94%) and MgCoSiO4 (>95%), together with minor amounts of WC (~3%) contaminant originating as debris abraded off milling balls and chambers. The macroscopic temperature monitoring of the grinding jars during milling trials recorded a peak temperature of 75 °C. A combination of analytical techniques that included XRD, TEM, SAED, and EDS were employed for the characterization of the synthesized products. 
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  8. Co 2 SiO 4 is a ceramic pigment and promising battery material of significant technological interest, as well as a model end-member of one of the most important mineral families in the Earth's crust and upper mantle. All previously developed methods for synthesis of Co 2 SiO 4 require high-temperature processing, which promotes grain growth, while the nanocrystalline form is required for some important technological applications. Here, we report a successful method for synthesizing nanocrystalline Co 2 SiO 4 via a simple and inexpensive high-energy ball milling mechanochemical process. Products of the synthesis were characterized by a combination of XRD and TEM, and their crystal structures and elemental compositions are reported. 
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