The Earth's core is believed to contain some light elements because it is 10% less dense than pure Fe under the corresponding pressure and temperature conditions. Hydrogen, a promising candidate among light elements, has phase relations and physical properties that have been investigated mainly for the Fe-H system. This study specifically examined an Fe-Si-H system using in-situ neutron diffraction experiments to investigate the site occupancy of deuterium of hcp-Fe0.95Si0.05 hydride at 14.7 GPa and 800 K. To date, this pressure condition is the highest for neutron diffraction experiments conducted at high pressure and high temperature, where crystal structure analysis has been conducted. Results of Rietveld refinement indicate hcp-Fe0.95Si0.05 hydride as having deuterium (D) occupancy of 0.24(2) exclusively at the interstitial octahedral site in the hcp lattice. The effect on the site occupancy of D by addition of 2.6 wt% Si into Fe (Fe0.95Si0.05) was negligible compared to results obtained from an earlier study of an Fe-D system (Machida et al., 2019).

Neutron powder diffraction profiles were collected for iron deuteride (FeDx) while the temperature decreased from 1023 to 300 K for a pressure range of 4–6 gigapascal (GPa). The ε′ deuteride with a double hexagonal close-packed (dhcp) structure, which coexisted with other stable or metastable deutrides at each temperature and pressure condition, formed solid solutions with a composition of FeD0.68(1) at 673 K and 6.1 GPa and FeD0.74(1) at 603 K and 4.8 GPa. Upon stepwise cooling to 300 K, the D-content x increased to a stoichiometric value of 1.0 to form monodeuteride FeD1.0. In the dhcp FeD1.0 at 300 K and 4.2 GPa, dissolved D atoms fully occupied the octahedral interstitial sites, slightly displaced from the octahedral centers in the dhcp metal lattice, and the dhcp sequence of close-packed Fe planes contained hcp-stacking faults at 12%. Magnetic moments with 2.11 ± 0.06 μB/Fe-atom aligned ferromagnetically in parallel on the Fe planes.

High-pressure responses of RbHCO3 and CsHCO3 were characterized by in situ Raman spectroscopy and X-ray and neutron diffraction observations. RbHCO3 exhibited a monoclinic (phase IV) and a triclinic (phase V) high-pressure phase at ~0.5 ​GPa and room temperature. Increasing compression induced unique behavior in a specific cell parameter (a in phase IV or c in phase V), which first increased, and then decreased at ~1 ​GPa, likely owing to the rearrangement of Rb+ and reconfiguration of the ordered (HCO3−)2 dimers. Deuterium positions in phase IV of RbDCO3 were determined. The hydrogen bonding remained moderately strong, and possibly did not affect the phase transition despite the accompanying disordering and ordering of the dimers. CsHCO3 showed no structural change up to 5 ​GPa, suggesting that its ambient phase (isostructural to phase IV of KHCO3) was already stable at high pressure. The structural stability appeared to be systematically related to the cation size.

Lawsonite is considered to be one of the most likely hydrous minerals to explain the persistence of seismic low-velocity layers (LVLs) atop subducted slabs to depths of 100–250 km due mainly to the fact that it can persist to these depths, in contrast to other hydrous minerals such as antigorite. However, as it is highly anisotropic and subjected to intense deformation during subduction, further constrains on the development of lawsonite crystal preferred orientation (CPO) at high pressure and temperature are required in order to evaluate its role in slowing seismic waves. We have deformed lawsonite aggregates at 5 GPa and 500–800 °C corresponding to 150 km depth and covering temperatures for both cold and hot subduction zones. In this study, we report a new lawsonite CPO pattern resulting from dislocation creep deformation that has not been previously observed. The [100] axes concentrate into the shear direction and the [010] axes are normal to the shear plane, respectively (we refer to this as “type-1” CPO). Such CPO is consistent with our transmission electron microscope (TEM) observations identifying (010)[100] as a dominant dislocation slip-system. The seismic properties resulting from this CPO show the fast P-wave direction to be parallel to the shear direction, and the slow P-wave direction and maximum S-wave anisotropy normal to the shear plane. We performed calculation of omphacite-lawsonite aggregates using our experimental data and varied both the lawsonite contents and the slab dipping angle. Our results show that a reasonable amount of lawsonite can explain Vs reduction in the LVLs, but cannot explain the Vp reduction. However, the presence of lawsonite would induce a rotation of the fast S-wave polarization toward the trench direction as the S-wave anisotropy increases or decreases according to the lawsonite proportion, its CPO strength and the slab dipping angle. We believe that our calculation can now be used for investigation of lawsonite effect in various subductions zones.

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Density of the Earth's core is lower than that of pure iron and the light element(s) in the core is a long-standing problem. Hydrogen is the most abundant element in the solar system and thus one of the important candidates. However, the dissolution process of hydrogen into iron remained unclear. Here we carry out high-pressure and high-temperature in situ neutron diffraction experiments and clarify that when the mixture of iron and hydrous minerals are heated, iron is hydrogenized soon after the hydrous mineral is dehydrated. This implies that early in the Earth's evolution, as the accumulated primordial material became hotter, the dissolution of hydrogen into iron occurred before any other materials melted. This suggests that hydrogen is likely the first light element dissolved into iron during the Earth's evolution and it may affect the behaviour of the other light elements in the later processes.

Ultrafine-grained (0.2-0.3μm) WC-Ni hardmetals with a low Ni content (3-5wt%) were developed using new production techniques based on adding an appropriate amount of VC and Cr3C2, combined with the strong mixing of raw materials. Their uniaxial compressibility was subsequently compared with that of existing WC-Ni and WC-Co hardmetals to assess their suitability for use as anvils in various high pressure experiments, particularly those associated with neutron or magnetic studies. The ultimate compressive strength of the newly developed hardmetals was over 7.7GPa, which was higher by 1.2GPa than that of the existing WC-Ni hardmetal MF10. When these hardmetals were used as anvils, a pressure of approximately 16GPa was generated using a Paris-Edinburgh-type apparatus with φ8mm culet, thereby proving that they can allow the physical properties of various materials to be measured at higher pressures than is possible with existing hardmetals.

X-ray radiography was applied to observe the segregation process of iron from silicate at high pressure and high temperature in mixtures containing light elements. As the temperature of the hydrogen-containing sample increases, the molten iron becomes coherent. Small droplets of iron sink to the bottom of the chamber, where they merge into a single, large droplet. The small iron droplets exhibit complex motion, moving in random directions. Markedly different behavior is found in the sulfur-containing sample, where no clear motion of the molten iron is observed. Instead, as the sample temperature is increased, the concentration of iron near the wall of the sample chamber gradually increases. These observations demonstrate that the behavior of molten iron changes according to the dissolved elements. This X-ray radiography experiment represents a powerful technique to study the segregation process of molten iron from solid or partially molten silicate, particularly when combined with high-resolution tomography techniques.

Three kinds of ceramics, zirconia-toughened alumina (ZTA), alumina-toughened zirconia (ATZ) and yttria-stabilized zirconia (YSZ), were tested as anvil materials, mainly for the purpose of neutron scattering study under high pressure. ZTA with non-toroidal anvil profile, having the same sample volume as conventionally used double toroidal anvils, sustained pressures up to 11.9GPa. This is comparable to anvils made of tungsten carbide (TC) with Ni binder with the same dimensions. ATZ would also be an alternative material to TC with pressure performance comparable to ZTA, whereas YSZ is much weaker than the other two ceramics. The attenuation coefficient for YSZ is significantly smaller than that of TC and similar to ZTA and ATZ, the latter being estimated by attenuation calculations. Neutron diffraction on a sample of lead in YSZ anvils as well as quasi-elastic neutron scattering on liquid water in ZTA also demonstrate the outstanding neutron transparency of these ceramics. The gain factor in count rate is up to one order of magnitude.

In situ neutron diffraction measurements combined with the pulsed neutron source at the Japan Proton Accelerator Research Complex (J-PARC) were conducted on high-pressure polymorphs of deuterated portlandite (Ca(OD)2) using a Paris-Edinburgh cell and a multi-anvil press. The atomic positions including hydrogen for the unquenchable high-pressure phase at room temperature (phase II′) were first clarified. The bent hydrogen bonds under high pressure were consistent with results from Raman spectroscopy. The structure of the high-pressure and high-temperature phase (Phase II) was concordant with that observed previously by another group for a recovered sample. The observations elucidate the phase transition mechanism among the polymorphs, which involves the sliding of CaO polyhedral layers, position modulations of Ca atoms, and recombination of Ca-O bonds accompanied by the reorientation of hydrogen to form more stable hydrogen bonds. © 2014 Elsevier Inc.

Hydrogen composition and occupation state provide basic information for understanding various properties of the metal-hydrogen system, ranging from microscopic properties such as hydrogen diffusion to macroscopic properties such as phase stability. Here the deuterization process of face-centred cubic Fe to form solid-solution face-centred cubic FeD x is investigated using in situ neutron diffraction at high temperature and pressure. In a completely deuterized specimen at 988 K and 6.3 GPa, deuterium atoms occupy octahedral and tetrahedral interstitial sites with an occupancy of 0.532(9) and 0.056(5), respectively, giving a deuterium composition x of 0.64(1). During deuterization, the metal lattice expands approximately linearly with deuterium composition at a rate of 2.21 Å3 per deuterium atom. The minor occupation of the tetrahedral site is thermally driven by the intersite movement of deuterium atoms along the 111 direction in the face-centred cubic metal lattice.

The crystal structure of a high-pressure phase of calcium hydroxide, Ca(OH)2 (portlandite), was clarified for the first time using the combination of in situ single-crystal and powder X ray diffraction measurements at high pressure and room temperature. A diamond-anvil cell with a wide opening angle and cell-assembly was improved for single-crystal X ray diffraction experiments, which allowed us to successfully observe Bragg reflections in a wide range of reciprocal space. The transition occurred at 6 GPa and the crystal structure of the high-pressure phase was determined to be monoclinic at 8.9 GPa and room temperature [I121; a = 5.8882(10), b = 6.8408(9), c = 8.9334(15) Å, β = 104.798(15)°]. The transition involved a decrease in molar volume by approximately 5.8%. A comparison of the structures of the low- and high-pressure phases indicates that the transition occurs by a shift of CaO 6 octahedral layers in the a-b plane along the a-axis, accompanied by up-and-down displacements of Ca atoms from the a-b plane. The crystal structure of this high-pressure phase is considered to be an intermediate state between the low-pressure phase and the high-pressure-high-temperature phase. The complicated diffraction patterns of the high-pressure phase suggest that the phase transition occurred toward three directions around the c-axis of the low-pressure phase. This explains the difficulties encountered in previous structural analyses. The present results will provide key information for discussing the behavior of hydrogen bonds in these hydrous minerals under pressure.

We designed new anvil assemblies for acquiring high-quality neutron diffraction data and ruby fluorescence spectra inside a sample chamber. The conical aperture of Ni-binded WC anvils was expanded by a factor of two. A hybrid gasket made of TiZr- and Al-alloy was developed to prevent outward extrusion. A small and optically transparent window of moissanite was introduced to allow for the determination of pressure and hydrostaticity by measurement of ruby fluorescence spectra. High pressure-generation tests that make use of Bi electrical conductivity and ruby pressure markers revealed that pressure could be determined over 10GPa. In situ synchrotron X-ray diffraction experiments were also carried out using NaCl as the pressure calibrants. The maximum pressure achieved was approximately 13GPa. The neutron diffraction intensity from the newly generated anvil assemblies was 2.5-3.0 times greater than that using the standard toroidal anvil assemblies used previously. © 2012 Copyright Taylor and Francis Group, LLC.

The pressure responses of portlandite and the isotope effect on the phase transition were investigated at room temperature from single-crystal Raman and IR spectra and from powder X-ray diffraction using diamond anvil cells under quasi-hydrostatic conditions in a helium pressure-transmitting medium. Phase transformation and subsequent peak broadening (partial amorphization) observed from the Raman and IR spectra of Ca(OH)2 occurred at lower pressures than those of Ca(OD)2. In contrast, no isotope effect was found on the volume and axial compressions observed from powder X-ray diffraction patterns. X-ray diffraction lines attributable to the high-pressure phase remained up to 28.5 GPa, suggesting no total amorphization in a helium pressure medium within the examined pressure region. These results suggest that the H-D isotope effect is engendered in the local environment surrounding H(D) atoms. Moreover, the ratio of sample-to-methanol-ethanol pressure medium (i.e., packing density) in the sample chamber had a significant effect on the increase in the half widths of the diffraction lines, even at pressures below the hydrostatic limit of the pressure medium. © 2011 Springer-Verlag.

A new opposed-anvil high pressure and temperature apparatus was developed based on the Drickamer-type apparatus. Various improvements were made to increase the sample volume and to generate high pressure and temperature stably and easily. By optimizing components such as the anvil, heater, and gasket, large sample volumes of about 4mm 3 (∼10 3 times more than that previously obtained with our previous apparatus) were achieved, with compact and light apparatus (outer diameter φ 40mm; height 31mm; weight 300g). Pressures and temperatures up to about 15GPa and 1700K can routinely and stably be achieved by using this assembly. In order to extend the pressure range further, sintered diamond was used as an anvil material. As a result, pressures and temperatures of around 38GPa and 1400K were achieved, although the sample volume was decreased to about 1.3∼10 -1mm 3. © 2011 Taylor and Francis.

We designed a new cell assembly of diamond anvil cells for single crystal x-ray diffraction under pressure and demonstrate the application of the cell to the crystallographic studies for ice VI and ethanol high-pressure (HP) phase at 0.95(5) GPa and 1.95(2) GPa, respectively. The features of the assembly are: (1) the platy anvil and unique-shaped backing seat (called as Wing seat) allowing the extremely wide opening angle up to ±65°, (2) the PFA-bulk metallic glass composite gasket allowing the easy attenuation correction and less background. Thanks to the designed assembly, the Rint values after attenuation corrections are fairly good (0.0125 and 0.0460 for ice VI and ethanol HP phase, respectively), and the errors of the refined parameters are satisfactory small even for hydrogen positions, those are comparable to the results which obtained at ambient conditions. The result for ice VI is in excellent agreement with the previous study, and that for ethanol HP phase has remarkable contributions to the revision to its structure; the H12 site, which makes gauche molecules with O1, C2, and C3 sites, may not exist so that only trans conformers are present at least at 1.95(2) GPa. The accurate intensities using the cell assembly allow us to extract the electron density for ethanol HP phase by the maximum entropy method. © 2011 American Institute of Physics.

Infrared absorption spectra of δ-AlOOH and its deuterated form (δ-AlOOD) were measured at high pressure using a diamond anvil cell under a quasi-hydrostatic pressure condition using helium as a pressure-transmitting medium. Two absorption bands at 1180 cm-1and 1330 cm-1 involving vibrations of hydrogen and oxygen atoms shifted to higher frequencies with increasing pressure up to 10 and 12 GPa for δ-AlOOH and δ-AlOOD, respectively. In contrast, at higher pressures the two bands did not shift so much. The pressure-response on the infrared spectra has a close relationship to the symmetrization of the hydrogen bonds and change in the compressibility which was observed from X-ray diffraction measurements. © 2010 IOP Publishing Ltd.

Ruby fluorescence spectra were statistically compared in between a 4:1 methanol-ethanol and its deuterated mixture under high pressure in the DAC. It was confirmed that the isotope substitution in the pressure transmitting media results in no distinctive difference in the peak shape and pressure shift of the R1 and R2 lines in the ruby fluorescence spectra up to around 25 GPa. These results suggest that the pressure-induced solidification/glass transition between these hydrogenated and deuterated liquids has no isotopic effect within experimental uncertainties. © 2010 IOP Publishing Ltd.

下部マントルまで水を運搬する可能性が示唆されている、含水アルミニウム水酸化物delta-AlOOHについて、疑似静水圧条件で圧縮率の精密測定と赤外吸収スペクトルの観察を行い、水素結合の対称化の兆候を観察した。また、圧力応答に水素の同位体効果が見られた。

The compression behaviors of δ-AlOOH and δ-AlOOD were investigated under quasi-hydrostatic conditions at pressures up to 63.5 and 34.9 GPa, respectively, using results from synchrotron X-ray diffraction experiments conducted at ambient temperature. Because of the geometric isotope effect, at ambient pressure, the a and b axes of δ-AlOOD, which define the plane in which the hydrogen bond lies, are longer than those of δ-AOOH. Under increasing pressure, the a and b axes of δ-AlOOH stiffen at 10 GPa, although the c axis shows no marked change. Identical behavior was found in δ-AlOOD, but the change in compressibility was observed at a slightly higher pressure of 12 GPa. Axial ratios a/c and b/c first decrease rapidly with increasing pressure, then begin to increase at pressures >10 GPa in δ-AlOOH and >12 GPa in δ-AlOOD. At these pressures, the pressure dependence of a/b also changes from increasing to decreasing. The unit-cell volumes of δ-AlOOH and δ-AlOOD become slightly less compressible at high pressures. Assuming K0' = 4, the calculated bulk moduli of δ-AlOOH below and above 10 GPa are 152(2) and 219(3) GPa, respectively. Those of δ-AlOOD below and above 12 GPa are 151(1) and 207(2) GPa, respectively.

A method was proposed for measuring infrared absorption spectra at high pressure under quasi-hydrostatic pressure conditions. Two KBr micro-pellets were prepared as samples, and reference materials were charged in a diamond anvil cell, applying helium as the pressure-transmitting medium. Using this method, the quasi-hydrostatic pressure condition was retained up to approximately 20GPa. Furthermore, hydrostaticity was much better than conventional pressure-transmitting media used for infrared spectroscopy. Infrared absorption spectra of α -FeOOH at high pressure were measured using the KBr micro-pellet method with a helium pressure-transmitting medium. Downshift of the OH stretching vibration was observed with increasing pressure. Use of the KBr micro-pellet method for infrared absorption spectroscopy at high pressure is a complementary experimental technique to neutron diffraction at high pressure for studying the pressure response of hydrogen bonds.