Submillisecond in situ X-ray diffraction measurement system with changing temperature and pressure using diamond anvil cells at BL10XU/SPring-8.

Recently, there has been a high demand for elucidating kinetics and visualizing reaction processes under extreme dynamic conditions, such as chemical reactions under meteorite impact conditions, structural changes under nonequilibrium conditions, and in situ observations of dynamic changes. To accelerate material science studies and Earth science fields under dynamic conditions, a submillisecond in situ X-ray diffraction measurement system has been developed using a diamond anvil cell to observe reaction processes under rapidly changing pressure and temperature conditions replicating extreme dynamic conditions. The development and measurements were performed at the high-pressure beamline BL10XU/SPring-8 by synchronizing a high-speed hybrid pixel array detector, laser heating and temperature measurement system, and gas-pressure control system that enables remote and rapid pressure changes using the diamond anvil cell. The synchronized system enabled momentary heating and rapid cooling experiments up to 5000 K via laser heating as well as the visualization of structural changes in high-pressure samples under extreme dynamic conditions during high-speed pressure changes.

Crystallization of silicon dioxide and compositional evolution of the Earth's core.

The Earth's core is about ten per cent less dense than pure iron (Fe), suggesting that it contains light elements as well as iron. Modelling of core formation at high pressure (around 40-60 gigapascals) and high temperature (about 3,500 kelvin) in a deep magma ocean predicts that both silicon (Si) and oxygen (O) are among the impurities in the liquid outer core. However, only the binary systems Fe-Si and Fe-O have been studied in detail at high pressures, and little is known about the compositional evolution of the Fe-Si-O ternary alloy under core conditions. Here we performed melting experiments on liquid Fe-Si-O alloy at core pressures in a laser-heated diamond-anvil cell. Our results demonstrate that the liquidus field of silicon dioxide (SiO2) is unexpectedly wide at the iron-rich portion of the Fe-Si-O ternary, such that an initial Fe-Si-O core crystallizes SiO2 as it cools. If crystallization proceeds on top of the core, the buoyancy released should have been more than sufficient to power core convection and a dynamo, in spite of high thermal conductivity, from as early on as the Hadean eon. SiO2 saturation also sets limits on silicon and oxygen concentrations in the present-day outer core.

A portable on-axis laser-heating system for near-90° X-ray spectroscopy: application to ferropericlase and iron silicide.

A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source and zero attenuation of incoming X-rays other than by the high-pressure environment. A description of the system, which has been tested for pressures above 100 GPa and temperatures up to 3000 K, is given. The XES spectra of laser-heated Mg0.67Fe0.33O demonstrate the potential to map the iron spin state in the pressure-temperature range of the Earth's lower mantle, and the NIS spectra of laser-heated FeSi give access to the sound velocity of this candidate of a phase inside the Earth's core. This portable system represents one of the few bridges across the gap between laser heating and high-resolution X-ray spectroscopies with signal collection near 90°.

Fate of MgSiO3 melts at core-mantle boundary conditions.

One key for understanding the stratification in the deep mantle lies in the determination of the density and structure of matter at high pressures, as well as the density contrast between solid and liquid silicate phases. Indeed, the density contrast is the main control on the entrainment or settlement of matter and is of fundamental importance for understanding the past and present dynamic behavior of the deepest part of the Earth's mantle. Here, we adapted the X-ray absorption method to the small dimensions of the diamond anvil cell, enabling density measurements of amorphous materials to unprecedented conditions of pressure. Our density data for MgSiO3 glass up to 127 GPa are considerably higher than those previously derived from Brillouin spectroscopy but validate recent ab initio molecular dynamics simulations. A fourth-order Birch-Murnaghan equation of state reproduces our experimental data over the entire pressure regime of the mantle. At the core-mantle boundary (CMB) pressure, the density of MgSiO3 glass is 5.48 ± 0.18 g/cm(3), which is only 1.6% lower than that of MgSiO3 bridgmanite at 5.57 g/cm(3), i.e., they are the same within the uncertainty. Taking into account the partitioning of iron into the melt, we conclude that melts are denser than the surrounding solid phases in the lowermost mantle and that melts will be trapped above the CMB.

Growth of submillimeter SrTaO2N single crystals by an NH3-assisted SrCl2 flux method.

Perovskite-type oxynitrides have recently been highlighted due to their dielectric and photocatalytic properties. Numerous studies have addressed the synthesis and characterization of their nanocrystals and ceramics. However, few research works have considered single-crystal formation in such systems due to difficulties in melt growth. In this study, we explore the crystal growth of perovskite-type oxynitride SrTaO2N by an NH3-assisted SrCl2 flux method. Submillimeter-sized single crystals with lengths of approximately 300 µm were grown at a temperature of 1200 °C for 10 h with a solute concentration of 1.5 mol%. Subsequently, the crystal growth mechanism of SrTaO2N in an SrCl2 flux was studied systematically through experiments with variable holding temperature, holding time, cooling rate, and solute concentration. Our results suggest that SrTaO2N crystal growth is induced by the evaporation of SrCl2 flux.

Author Correction: Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Perovskite in Earth's deep interior.

Silicate perovskite-type phases are the most abundant constituent inside our planet and are the predominant minerals in Earth's lower mantle more than 660 kilometers below the surface. Magnesium-rich perovskite is a major lower mantle phase and undergoes a phase transition to post-perovskite near the bottom of the mantle. Calcium-rich perovskite is proportionally minor but may host numerous trace elements that record chemical differentiation events. The properties of mantle perovskites are the key to understanding the dynamic evolution of Earth, as they strongly influence the transport properties of lower mantle rocks. Perovskites are expected to be an important constituent of rocky planets larger than Mars and thus play a major role in modulating the evolution of terrestrial planets throughout the universe.

Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure.

Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions. By means of single crystal X-ray diffraction we determined that Fe7O9 adopts a monoclinic C2/m lattice with the most distorted crystal structure among the binary iron oxides known to date. The synthesis of Fe7O9 opens a new portal to exotic iron-rich (M,Fe)7O9 oxides with unusual stoichiometry and distorted crystal structures. Moreover, the crystal structure and phase relations of such new iron oxide groups may provide new insight into the cycling of volatiles in the Earth's interior.

Stability of Fe,Al-bearing bridgmanite in the lower mantle and synthesis of pure Fe-bridgmanite.

The physical and chemical properties of Earth's mantle, as well as its dynamics and evolution, heavily depend on the phase composition of the region. On the basis of experiments in laser-heated diamond anvil cells, we demonstrate that Fe,Al-bearing bridgmanite (magnesium silicate perovskite) is stable to pressures over 120 GPa and temperatures above 3000 K. Ferric iron stabilizes Fe-rich bridgmanite such that we were able to synthesize pure iron bridgmanite at pressures between ~45 and 110 GPa. The compressibility of ferric iron-bearing bridgmanite is significantly different from any known bridgmanite, which has direct implications for the interpretation of seismic tomography data.

The advanced ion-milling method for preparation of thin film using ion slicer: application to a sample recovered from diamond-anvil cell.

The advanced argon ion-milling technique using a new instrument called ion slicer was newly developed for preparation of thin foil. Compared to the conventional ion-milling methods, this technique facilitates very wide area to be homogeneously thinned by rocking the ion beam source with low angle and the specimen during milling. Here we applied this technique to a sample recovered from a laser-heated diamond-anvil cell (DAC). We obtained the thin film of almost entire cross section of the DAC sample along the compression axis, which possesses of approximately (10x50) microm(2). The laser-heated sample is often heterogeneous due to a large temperature gradient. However the chemical analyses are obtained from the whole hot spot under the transmission electron microscope by preparing the thin foil using the ion slicer.

The electrical conductivity of post-perovskite in Earth's D'' layer.

Recent discovery of a phase transition from perovskite to post-perovskite suggests that the physical properties of Earth's lowermost mantle, called the D'' layer, may be different from those of the overlying mantle. We report that the electrical conductivity of (Mg0.9Fe0.1)SiO3 post-perovskite is >10(2) siemens per meter and does not vary greatly with temperature at the conditions of the D'' layer. A post-perovskite layer above the core-mantle boundary would, by electromagnetic coupling, enhance the exchange of angular momentum between the fluid core and the solid mantle, which can explain the observed changes in the length of a day on decadal time scales. Heterogeneity in the conductivity of the lowermost mantle is likely to depend on changes in chemistry of the boundary region, not fluctuations in temperature.