Riko Iizuka

Change in compressibility of δ-AlOOH and δ-AlOOD at high pressure: A study of isotope effect and hydrogen-bond symmetrization

Abstract 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.

Site occupancy of interstitial deuterium atoms in face-centred cubic iron.

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 FeDx 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.

An opposed-anvil-type apparatus with an optical window and a wide-angle aperture for neutron diffraction

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 10 GPa. In situ synchrotron X-ray diffraction experiments were also carried out using NaCl as the pressure calibrants. The maximum pressure achieved was approximately 13 GPa. 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.

Comparing ruby fluorescence spectra at high pressure in between methanol-ethanol pressure transmitting medium and its deuteride

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.

Infrared absorption spectra of δ-AlOOH and its deuteride at high pressure and implication to pressure response of the hydrogen bonds

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.

Performance of ceramic anvils for high pressure neutron scattering

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 11.9 GPa. 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.

A simple opposed-anvil apparatus for high pressure and temperature experiments above 10 GPa

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 4 mm3 (∼103 times more than that previously obtained with our previous apparatus) were achieved, with compact and light apparatus (outer diameter ϕ 40 mm; height 31 mm; weight 300 g). Pressures and temperatures up to about 15 GPa and 1700 K 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 38 GPa and 1400 K were achieved, although the sample volume was decreased to about 1.3×10−1 mm3.

Micro-pellet method for infrared absorption spectroscopy using a diamond anvil cell under a quasi-hydrostatic condition

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 20 GPa. 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.

Application of X-ray radiography to study the segregation process of iron from silicate under high pressure and high temperature

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.

Crystal structure of the high-pressure phase of calcium hydroxide, portlandite: In situ powder and single-crystal X-ray diffraction study

Abstract 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 CaO6 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.