In situ high-pressure pair distribution function measurement of liquid and glass by using 100 keV pink beam.

Understanding the pressure-induced structural changes in liquids and amorphous materials is fundamental in a wide range of scientific fields. However, experimental investigation of the structure of liquid and amorphous material under in situ high-pressure conditions is still limited due to the experimental difficulties. In particular, the range of the momentum transfer (Q) in the structure factor [S(Q)] measurement under high-pressure conditions has been limited at relatively low Q, which makes it difficult to conduct detailed structural analysis of liquid and amorphous material. Here, we show the in situ high-pressure pair distribution function measurement of liquid and glass by using the 100 keV pink beam. Structures of liquids and glasses are measured under in situ high-pressure conditions in the Paris-Edinburgh press by high-energy x-ray diffraction measurement using a double-slit collimation setup with a point detector. The experiment enables us to measure S(Q) of GeO2 and SiO2 glasses and liquid Ge at a wide range of Q up to 20-29 Å-1 under in situ high-pressure and high-temperature conditions, which is almost two times larger than that of the conventional high-pressure angle-dispersive x-ray diffraction measurement. The high-pressure experimental S(Q) precisely determined at a wide range of Q opens the way to investigate detailed structural features of liquids and amorphous materials under in situ high-pressure and high-temperature conditions, as well as ambient pressure study.

Effect of water on seismic attenuation of the upper mantle: The origin of the sharp lithosphere-asthenosphere boundary.

Oceanic lithosphere moves over a mechanically weak layer (asthenosphere) characterized by low seismic velocity and high attenuation. Near mid-ocean ridges, partial melting can produce such conditions because of the high-temperature geotherm. However, seismic observations have also shown a large and sharp velocity reduction under oceanic plates at the lithosphere-asthenosphere boundary (LAB) far from mid-ocean ridges. Here, we report the effect of water on the seismic properties of olivine aggregates in water-undersaturated conditions at 3 GPa and 1,223 to 1,373 K via in-situ X-ray observation using cyclic loading. Our results show that water substantially enhances the energy dispersion and reduces the elastic moduli over a wide range of seismic frequencies (0.5 to 1,000 s). An attenuation peak that appears at higher frequencies (1 to 5 s) becomes more pronounced as the water content increases. If water exists only in the asthenosphere, this is consistent with the observation that the attenuation in the asthenosphere is almost constant over a wide frequency range. These sharp seismic changes at the oceanic LAB far from mid-ocean ridges could be explained by the difference in water content between the lithosphere and asthenosphere.

In situ X-ray and acoustic observations of deep seismic faulting upon phase transitions in olivine.

The activity of deep-focus earthquakes, which increases with depth from ~400 km to a peak at ~600 km, is enigmatic, because conventional brittle failure is unlikely to occur at elevated pressures. It becomes increasingly clear that pressure-induced phase transitions of olivine are responsible for the occurrence of the earthquakes, based on deformation experiments under pressure. However, many such experiments were made using analogue materials and those on mantle olivine are required to verify the hypotheses developed by these studies. Here we report the results of deformation experiments on (Mg,Fe)2SiO4 olivine at 11-17 GPa and 860-1350 K, equivalent to the conditions of the slabs subducted into the mantle transition zone. We find that throughgoing faulting occurs only at very limited temperatures of 1100-1160 K, accompanied by intense acoustic emissions at the onset of rupture. Fault sliding aided by shear heating occurs along a weak layer, which is formed via linking-up of lenticular packets filled with nanocrystalline olivine and wadsleyite. Our study suggests that transformational faulting occurs on the isothermal surface of the metastable olivine wedge in slabs, leading to deep-focus earthquakes in limited regions and depth range.

Highly Electron-Doped TaON Single-Crystal Growth by a High-Pressure Flux Method.

Transition-metal oxynitrides have a variety of functions such as visible light-responsive catalysts and dielectric materials, but acquiring single crystals necessary to understand inherent properties is difficult and is limited to relatively small sizes (<10 µm) because they easily decompose at high temperatures. Here, we have succeeded in growing platelet single crystals of TaON with a typical size of 50 × 100 × 10 µm3 under a high pressure and high temperature (6 GPa and 1400 °C) using a LiCl flux. Such a harsh condition, in contrast to powder samples synthesized under mild conditions, resulted in the introduction of a large amount of oxygen vacancies (x = 0.06 in TaO1-xN) into the crystal, providing a metallic behavior with a large anisotropy of ρc/ρab ∼ 103. Low-temperature oxygen annealing allows for a single-crystal-to-single-crystal transformation to obtain fully oxidized TaON (yellow) crystals. Needle-like crystals can be obtained when NH4Cl is used as a flux. Furthermore, black Hf2ON2 single crystals are also grown, suggesting that the high-pressure flux method is widely applicable to other transition-metal oxynitrides, with extensive carrier control.

Experimental evidence of tetrahedral symmetry breaking in SiO2 glass under pressure.

Bimodal behavior in the translational order of silicon's second shell in SiO2 liquid at high temperatures and high pressures has been recognized in theoretical studies, and the fraction of the S state with high tetrahedrality is considered as structural origin of the anomalous properties. However, it has not been well identified in experiment. Here we show experimental evidence of a bimodal behavior in the translational order of silicon's second shell in SiO2 glass under pressure. SiO2 glass shows tetrahedral symmetry structure with separation between the first and second shells of silicon at low pressures, which corresponds to the S state structure reported in SiO2 liquid. On the other hand, at high pressures, the silicon's second shell collapses onto the first shell, and more silicon atoms locate in the first shell. These observations indicate breaking of local tetrahedral symmetry in SiO2 glass under pressure, as well as SiO2 liquid.

Viscosity of bridgmanite determined by in situ stress and strain measurements in uniaxial deformation experiments.

To understand mantle dynamics, it is important to determine the rheological properties of bridgmanite, the dominant mineral in Earth's mantle. Nevertheless, experimental data on the viscosity of bridgmanite are quite limited due to experimental difficulties. Here, we report viscosity and deformation mechanism maps of bridgmanite at the uppermost lower mantle conditions obtained through in situ stress-strain measurements of bridgmanite using deformation apparatuses with the Kawai-type cell. Bridgmanite would be the hardest among mantle constituent minerals even under nominally dry conditions in the dislocation creep region, consistent with the observation that the lower mantle is the hardest layer. Deformation mechanism maps of bridgmanite indicate that grain size of bridgmanite and stress conditions at top of the lower mantle would be several millimeters and ~105 Pa to realize viscosity of 1021-22 Pa·s, respectively. This grain size of bridgmanite suggests that the main part of the lower mantle is isolated from the convecting mantle as primordial reservoirs.

Depressed 660-km discontinuity caused by akimotoite-bridgmanite transition.

The 660-kilometre seismic discontinuity is the boundary between the Earth's lower mantle and transition zone and is commonly interpreted as being due to the dissociation of ringwoodite to bridgmanite plus ferropericlase (post-spinel transition)1-3. A distinct feature of the 660-kilometre discontinuity is its depression to 750 kilometres beneath subduction zones4-10. However, in situ X-ray diffraction studies using multi-anvil techniques have demonstrated negative but gentle Clapeyron slopes (that is,  the ratio between pressure and temperature changes) of the post-spinel transition that do not allow a significant depression11-13. On the other hand, conventional high-pressure experiments face difficulties in accurate phase identification due to inevitable pressure changes during heating and the persistent presence of metastable phases1,3. Here we determine the post-spinel and akimotoite-bridgmanite transition boundaries by multi-anvil experiments using in situ X-ray diffraction, with the boundaries strictly based on the definition of phase equilibrium. The post-spinel boundary has almost no temperature dependence, whereas the akimotoite-bridgmanite transition has a very steep negative boundary slope at temperatures lower than ambient mantle geotherms. The large depressions of the 660-kilometre discontinuity in cold subduction zones are thus interpreted as the akimotoite-bridgmanite transition. The steep negative boundary of the akimotoite-bridgmanite transition will cause slab stagnation (a stalling of the slab's descent) due to significant upward buoyancy14,15.

Simultaneous generation of ultrahigh pressure and temperature to 50 GPa and 3300 K in multi-anvil apparatus.

We attempted to generate ultrahigh pressure and temperature simultaneously using a multi-anvil apparatus by combining the technologies of ultrahigh-pressure generation using sintered diamond (SD) anvils, which can reach 120 GPa, and ultrahigh-temperature generation using a boron-doped diamond (BDD) heater, which can reach 4000 K. Along with this strategy, we successfully generated a temperature of 3300 K and a pressure of above 50 GPa simultaneously. Although the high hardness of BDD significantly prevents high-pressure generation at low temperatures, its high-temperature softening allows for effective pressure generation at temperatures above 1200 K. High temperature also enhances high-pressure generation because of the thermal pressure. We expect to generate even higher pressure in the future by combining SD anvils and a BDD heater with advanced multi-anvil technology.

Boron-MgO composite as an X-ray transparent pressure medium in the multi-anvil apparatus.

X-ray transparent materials are very beneficial for in situ X-ray experiments in the multi-anvil apparatus. We sintered machinable blocks of boron-MgO composites at 800-1000 °C under atmospheric pressure from a mixture of amorphous boron and brucite or Mg(OH)2. The machinability of composite blocks improved with an increase in the brucite content in the starting material; a brucite content higher than 15 wt. % showed reasonable machinability in forming various shapes such as octahedron, cylinder, and sleeve. We confirmed the feasibility of the boron-MgO pressure medium by successfully generating lower mantle pressure (>23 GPa); its pressure generation efficiency is comparable to that of a Cr2O3 doped MgO pressure medium. The boron-MgO composite is expected to be an excellent thermal insulator owing to the extremely low thermal conductivity of amorphous boron; we confirmed its better thermal insulation performance through a comparative heating test with a zirconia sleeve in a Cr2O3 doped MgO pressure medium. Constituting light elements, the boron-MgO composite has high X-ray transparency, which enables us to conduct various cutting edge X-ray measurements in the large volume multi-anvil apparatus.

Effect of sulfur on sound velocity of liquid iron under Martian core conditions.

Sulfur has been considered to be a predominant light element in the Martian core, and thus the sound velocity of Fe-S alloys at relevant high pressure and temperature is of great importance to interpret its seismological data. Here we measured the compressional sound velocity (VP) of liquid Fe, Fe80S20 and Fe57S43 using ultrasonic pulse-echo overlap method combined with a Kawai-type multi-anvil apparatus up to 20 GPa, likely corresponding to the condition at the uppermost core of Mars. The results demonstrate that the VP of liquid iron is least sensitive to its sulfur concentration in the Mars' whole core pressure range. The comparison of seismic wave speeds of Fe-S liquids with future observations will therefore tell whether the Martian core is molten and contains impurity elements other than sulfur.

Formation of bridgmanite-enriched layer at the top lower-mantle during magma ocean solidification.

Thermochemical heterogeneities detected today in the Earth's mantle could arise from ongoing partial melting in different mantle regions. A major open question, however, is the level of chemical stratification inherited from an early magma-ocean (MO) solidification. Here we show that the MO crystallized homogeneously in the deep mantle, but with chemical fractionation at depths around 1000 km and in the upper mantle. Our arguments are based on accurate measurements of the viscosity of melts with forsterite, enstatite and diopside compositions up to ~30 GPa and more than 3000 K at synchrotron X-ray facilities. Fractional solidification would induce the formation of a bridgmanite-enriched layer at ~1000 km depth. This layer may have resisted to mantle mixing by convection and cause the reported viscosity peak and anomalous dynamic impedance. On the other hand, fractional solidification in the upper mantle would have favored the formation of the first crust.

Sound velocity of CaSiO3 perovskite suggests the presence of basaltic crust in the Earth's lower mantle.

Laboratory measurements of sound velocities of high-pressure minerals provide crucial information on the composition and constitution of the deep mantle via comparisons with observed seismic velocities. Calcium silicate (CaSiO3) perovskite (CaPv) is a high-pressure phase that occurs at depths greater than about 560 kilometres in the mantle1 and in the subducting oceanic crust2. However, measurements of the sound velocity of CaPv under the pressure and temperature conditions that are present at such depths have not previously been performed, because this phase is unquenchable (that is, it cannot be physically recovered to room conditions) at atmospheric pressure and adequate samples for such measurements are unavailable. Here we report in situ X-ray diffraction and ultrasonic-interferometry sound-velocity measurements at pressures of up to 23 gigapascals and temperatures of up to 1,700 kelvin (similar to the conditions at the bottom of the mantle transition region) using sintered polycrystalline samples of cubic CaPv converted from bulk glass and a multianvil apparatus. We find that cubic CaPv has a shear modulus of 126 ± 1 gigapascals (uncertainty of one standard deviation), which is about 26 per cent lower than theoretical predictions3,4 (about 171 gigapascals). This value leads to substantially lower sound velocities of basaltic compositions than those predicted for the pressure and temperature conditions at depths between 660 and 770 kilometres. This suggests accumulation of basaltic crust in the uppermost lower mantle, which is consistent with the observation of low-seismic-velocity signatures below 660 kilometres5,6 and the discovery of CaPv in natural diamond of super-deep origin7. These results could contribute to our understanding of the existence and behaviour of subducted crust materials in the deep mantle.

Complete agreement of the post-spinel transition with the 660-km seismic discontinuity.

The 660-km seismic discontinuity, which is a significant structure in the Earth's mantle, is generally interpreted as the post-spinel transition, as indicated by the decomposition of ringwoodite to bridgmanite + ferropericlase. All precise high-pressure and high-temperature experiments nevertheless report 0.5-2 GPa lower transition pressures than those expected at the discontinuity depth (i.e. 23.4 GPa). These results are inconsistent with the post-spinel transition hypothesis and, therefore, do not support widely accepted models of mantle composition such as the pyrolite and CI chondrite models. Here, we present new experimental data showing post-spinel transition pressures in complete agreement with the 660-km discontinuity depth obtained by high-resolution in situ X-ray diffraction in a large-volume high-pressure apparatus with a tightly controlled sample pressure. These data affirm the applicability of the prevailing mantle models. We infer that the apparently lower pressures reported by previous studies are experimental artefacts due to the pressure drop upon heating. The present results indicate the necessity of reinvestigating the position of mantle mineral phase boundaries previously obtained by in situ X-ray diffraction in high-pressure-temperature apparatuses.

Simultaneous high-pressure high-temperature elastic velocity measurement system up to 27 GPa and 1873 K using ultrasonic and synchrotron X-ray techniques.

A new pulse-echo interferometry system has been developed for measurements of sound velocity at simultaneous high pressure and temperature corresponding to those of the Earth's lower mantle, using synchrotron X-ray techniques at SPring-8. A combination of a low-noise high-frequency amplifier and a high-speed solid-state relay system allowed us to clearly detect the ultrasonic echoes of a small sample (<1.0 mm in diameter and length) in multi-anvil apparatus. A new high-pressure cell has also been introduced for precise measurement of the length of the tiny sample by X-ray radiography imaging under very high pressure and temperature. The new system was tested by measuring elastic velocities of α-Al2O3 over wide pressure and temperature ranges of up to 27 GPa and 1873 K, respectively. The resultant adiabatic bulk modulus, shear modulus, and pressure and temperature derivatives of α-Al2O3 are K0S = 251.2 (18) GPa, ∂KS/∂P = 4.21 (10), ∂KS/∂T = -0.025 (1), G = 164.1 (7), ∂G/∂P = 1.59 (3), ∂G/∂T = -0.021 (1). These values are consistent with those previously reported based on experiments at high temperatures at ambient pressure and high pressures at room temperature. The present system allows precise measurements of the elastic velocities of minerals under the pressures and temperatures corresponding to the lower mantle for the first time, which should greatly contribute to our understanding of mineralogy of the whole mantle.

Synthesis of boron-doped diamond and its application as a heating material in a multi-anvil high-pressure apparatus.

We developed methods to use synthesized boron-doped diamond (BDD) as a heater in a multi-anvil high-pressure apparatus. The synthesized BDD heater could stably generate an ultra-high temperature without the issues (anomalous melt, pressure drop, and instability of heating) arising from oxidation of boron into boron oxide and graphite-diamond conversion. We synthesized BDD blocks and tubes with boron contents of 0.5-3.0 wt. % from a mixture of graphite and amorphous boron at 15 GPa and 2000 °C. The electrical conductivity of BDD increased with increasing boron content. The stability of the heater and heating reproducibility were confirmed through repeated cycles of heating and cooling. Temperatures as high as ∼3700 °C were successfully generated at higher than 10 GPa using the BDD heater. The effect of the BDD heater on the pressure-generation efficiency was evaluated using MgO pressure scale by in situ X-ray diffraction study at the SPring-8 synchrotron. The pressure-generation efficiency was lower than that using a graphite-boron composite heater up to 1500 tons. The achievement of stable temperature generation above 3000 °C enables melting experiments of silicates and determination of some physical properties (such as viscosity) of silicate melts under the Earth's lower mantle conditions.

Short-period cyclic loading system for in situ X-ray observation of anelastic properties at high pressure.

To determine the anelastic properties of materials of the Earth's interior, a short-period cyclic loading system was installed for in situ X-ray radiographic observation under high pressure to the multi-anvil deformation DIA press at the bending magnet beam line BL04B1 at SPring-8. The hydraulic system equipped with a piston controlled by a solenoid was designed so as to enable producing smooth sinusoidal stress in a wide range of oscillation period from 0.2 to 100 s and generating variable amplitudes. Time resolved X-ray radiography imaging of the sample and reference material provides their strain as a function of time during cyclic loading. A synchrotron X-ray radiation source allows us to resolve their strain variation with time even at the short period (<1 s). The minimum resolved strain is as small as 10-4, and the shortest oscillation period to detect small strain is 0.5 s. Preliminary experimental results exhibited that the new system can resolve attenuation factor Q-1 at upper mantle conditions. These results are in quantitative agreement with previously reported data obtained at lower pressures.

Mantle dynamics inferred from the crystallographic preferred orientation of bridgmanite.

Seismic shear wave anisotropy is observed in Earth's uppermost lower mantle around several subducted slabs. The anisotropy caused by the deformation-induced crystallographic preferred orientation (CPO) of bridgmanite (perovskite-structured (Mg,Fe)SiO3) is the most plausible explanation for these seismic observations. However, the rheological properties of bridgmanite are largely unknown. Uniaxial deformation experiments have been carried out to determine the deformation texture of bridgmanite, but the dominant slip system (the slip direction and plane) has not been determined. Here we report the CPO pattern and dominant slip system of bridgmanite under conditions that correspond to the uppermost lower mantle (25 gigapascals and 1,873 kelvin) obtained through simple shear deformation experiments using the Kawai-type deformation-DIA apparatus. The fabrics obtained are characterized by [100] perpendicular to the shear plane and [001] parallel to the shear direction, implying that the dominant slip system of bridgmanite is [001](100). The observed seismic shear- wave anisotropies near several subducted slabs (Tonga-Kermadec, Kurile, Peru and Java) can be explained in terms of the CPO of bridgmanite as induced by mantle flow parallel to the direction of subduction.

In-line System to Produce High-Purity Acid Solutions.

Herein, we report a new device that generates a high-purity acid solution. It comprises three compartments divided by anion-exchange membranes and filled with ion-exchange resins. Fluorochemical cation-exchange membranes, which tolerate electrochemical wear and permit bulk flow, are inserted between each electrode and the anion-exchange resin. A bipolar boundary is a composite boundary comprising anion and cation exchangers. This device has four bipolar boundaries to separate the location of acid generation from the location where water is electrolyzed. It can tolerate high pressures, resist degradation due to electrolysis at the electrodes, and produce high-purity acid solutions that are free from gases and cationic impurities. The acid solution is generated on the basis of an electrokinetic phenomenon at the surfaces of ion-exchange resins and membranes in an electric field; its concentration can be controlled at rates from 0.01 to 100 µmol/min by adjusting the electrical current applied to the device.