High pressure metal-silicate partitioning of Ni, Co, V, Cr, Si, and O, Geochimica et Cosmochimica Acta (2015), doi: http://dx.High pressure metal-silicate partitioning of Ni, Co, V, Cr, Si, and O AbstractThe distributions of major and minor elements in Earth's core and mantle were primarily established by high pressure, high temperature metal-silicate partitioning during core segregation. The partitioning behaviors of moderately siderophile elements can be used to constrain the pressure-temperature conditions of core formation and the 2 core's composition. We performed experiments to study the partitioning of Ni, Co, V, Cr, Si, and O between silicate melt and Fe-rich metallic melt in a multianvil press and diamond anvil cell, up to 100 GPa and 5700 K. Combining our new results with data from 18 previous studies, we parameterized the effects of pressure, temperature, and metallic melt composition on partitioning. Ni and Co partitioning are insensitive to composition. At low pressures, these elements become less siderophile with increasing temperature, with this trend reversing above ~45 GPa. V and Cr partitioning are much more sensitive to metallic melt composition and less sensitive to pressure. Partitioning of Si and O are insensitive to pressure, but with strong and moderate temperature dependences, respectively. Our new parameterizations of Ni and Co partitioning suggest that the Earth's distributions of these elements can be matched by single-stage coremantle equilibration at 54 ± 5 GPa and 3300-3400 K. These conditions would result in 8.5 ± 1.4 wt% Si and 1.6 ± 0.3 wt% O in the core, compatible with the core's measured density. However, this single-stage model matches the Earth's V and Cr distributions less well. We also incorporated our parameterizations into models of multi-stage core formation over evolving pressure-temperature-oxygen fugacity conditions, reproducing the Earth's Ni and Co distributions while simultaneously producing a core whose light element composition is consistent with its density.

Phase transitions and the chemical composition of minerals in Earth's interior influence geophysical interpretations of its deep structure and dynamics. A pressure-induced spin transition in olivine has been suggested to influence iron partitioning and depletion, resulting in a distinct layered structure in Earth's lower mantle. For a more realistic mantle composition (pyrolite), we observed a considerable change in the iron-magnesium partition coefficient at about 40 gigapascals that is explained by a spin transition at much lower pressures. However, only a small depletion of iron is observed in the major high-pressure phase (magnesium silicate perovskite), which may be explained by preferential retention of the iron ion Fe3+. Changes in mineral proportions or density are not associated with the change in partition coefficient. The observed density profile agrees well with seismological models, which suggests that pyrolite is a good model composition for the upper to middle parts of the lower mantle.

Homogeneous alloy nanoparticles as excellent catalysts. Spherical polyelectrolyte brushes can be used to generate Au‐Pt alloy nanoparticles (see figure) that exhibit properties widely differing from the properties of the respective bulk alloys. The alloy nanoparticles are shown to be homogeneous solid solutions. Moreover, they are effective catalysts for the selective oxidation of alcohols to aldehydes and ketones.

An orthorhombic (space group Pnnm) boron phase was synthesized at pressures above 9 GPa and high temperature, and it was demonstrated to be stable at least up to 30 GPa. The structure, determined by single-crystal x-ray diffraction, consists of B12 icosahedra and B2 dumbbells. The charge density distribution obtained from experimental data and ab initio calculations suggests covalent chemical bonding in this phase. Strong covalent interatomic interactions explain the low compressibility value (bulk modulus is K300=227 GPa) and high hardness of high-pressure boron (Vickers hardness HV=58 GPa), after diamond the second hardest elemental material.

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The authors report a synthesis of unique superhard aggregated boron nitride nanocomposites (ABNNCs) showing the enhancement of hardness up to 100% in comparison with single crystal c-BN. Such a great hardness increase is due to the combination of the Hall-Petch and the quantum confinement effects. The decrease of the grain size down to 14nm and the simultaneous formation of the two dense BN phases with hexagonal and cubic structures within the grains at nano- and subnanolevel result in enormous mechanical property enhancement with maximum hardness of 85(5)GPa. Thus, ABNNC is the first non-carbon-based bulk material with the value of hard-ness approaching that of single crystal and polycrystalline diamond and aggregated diamond nanorods. ABNNC also has an unusually high fracture toughness for superhard materials (K1C=15MPam0.5) and wear resistance (WH=11; compare, for industrial polycrystalline diamond, WH=3–4), in combination with high thermal stability (above 1600K in air), making it an exceptional superabrasive.

[1] Experiments to investigate the partitioning of oxygen between liquid iron and (Mg,Fe)O magnesiowüstite were conducted at 30-70 GPa and 2800-3500 K using a laser-heated diamond anvil cell. A thin foil was prepared from the reacted regions in the recovered samples using a focused ion beam. The compositions of coexisting quenched iron and magnesiowüstite were measured using a transmission electron microscope equipped with energy dispersive X-ray spectroscopy and electron energy-loss spectroscopy. In order to understand and model the results, additional experiments were performed to determine the activity of oxygen, or rather FeO, in liquid Fe metal. Multianvil experiments to measure the oxygen contents of coexisting immiscible metallic and ionic liquids in the Fe-FeO system were performed up to 25 GPa. The results were used to extract excess mixing properties for Fe-FeO liquids at high pressure and temperature. These properties were used to derive a model that describes oxygen partitioning in the Fe-Mg-O system that is independent of the actual experimental partitioning data. The model indicates that the oxygen content of liquid Fe becomes a strong nonlinear function of the FeO content of magnesiowüstite at pressures greater than 25 GPa. This prediction is in excellent agreement with the experimental partitioning data, which is faithfully reproduced in most instances. The new results confirm that the Earth's core is undersaturated in oxygen with respect to the FeO content of the bulk mantle, which will result either in FeO being depleted from the very base of the mantle or lead to the development of an FeO-enriched outer layer of the core. These possibilities are not mutually exclusive.

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