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Molybdenum nitride Mo3N5 with higher coordinates of molybdenum sites and an N–N dimer was synthesized under a high pressure of above 45 GPa.

We report the first synthesis of CuAl2-type VN2 and experimental investigation of the valence state for vanadium ions in VN2.

A novel high-pressure molybdenum nitride phase, Mo

A Nowotny chimney-ladder (NCL) chromium germanide (CrGeγ) with varying compositions has been synthesized under high pressure. Crystal structure parameters of the NCL CrGeγ have been calculated by Le Bail refinement based on the superspace group. The refined γ of CrGeγ increases with the synthesis pressure, indicating an increasing Ge content. The NCL CrGeγ phases are ferromagnetic at T = 2 K regardless of their composition, and the magnetic transition temperature (TC) increases when the γ becomes higher. It is noteworthy that CrGe1.763 and CrGe1.774 synthesized at P = 10 and 14 GPa have magnetic transition temperatures of T = 295 and 333 K above room temperature, respectively. Surprisingly, the magnetic transition temperature has changed by ΔTC = 270 K, although the γ values of the raw material and the sample synthesized at P = 14 GPa differ by only Δγ = 0.05, corresponding to an atomic concentration of 0.62 atom %. The synthesis pressure acts as an essential parameter in tuning the composition of the NCL phase. Accordingly, the high-pressure synthesis may significantly control several physical characteristics of NCL phases by utilizing compositional and structural modulation.

Tungsten nitride continues to drive fundamental interests because of its potential as a functional compound, which combines features such as high hardness together with thermal, chemical, and wear resistance. Here, we report a novel tungsten nitride phase synthesized from MoC-type WN0.6 and molecular nitrogen after laser irradiation at P = 70 GPa in a diamond anvil cell. This novel phase is quenchable at ambient pressure and determined to be U7Te12-type tungsten nitride and crystallizes in the hexagonal space group (P6) having lattice parameters of a = 8.2398(3) A, c = 2.94948(14) A, and V = 173.423(13) A3. Tungsten atoms are coordinated to eight and nine nitrogen atoms, higher than previously reported tungsten nitrides. The bulk modulus is determined to be K0 = 312 (5) GPa (K0' = 4.0 fixed), and DFT calculations predict that U7Te12-type W7N12 has a metallic nature.

Chromium germanides, namely, Nowotny chimney-ladder-phase CrGe1.77 and MoSi2-type CrGe2, were synthesized above 15 GPa or more via laser heating using a diamond anvil cell (LHDAC). MoSi2-type CrGe2, which is the most Ge-rich compound in the Cr-Ge system, crystallizes in the tetragonal structure with a space group of I4/mmm (no. 139) and lattice parameters of a = 3.24919(6) A and c = 8.0523(3) A and is isostructural with MoSi2. MoSi2-type CrGe2 has a deep pseudogap caused by the splitting of 3d orbitals with Cr, as evidenced by ab initio calculation. In this article, we have succeeded in synthesizing a binary compound between transition-metal and metalloid elements for the first time at high pressures above 10 GPa using the LHDAC. This pathway opens the possibility to explore more compounds in this system and may provide new insights into the fundamental interaction between these two elements.

A novel niobium nitride, U2S3-type Nb2N3, has been successfully synthesized by nitridation of δ-NbN above approximately 30 GPa in a laser-heated diamond anvil cell. Nb2N3 crystallizes in the same orthorhombic structure (space group: Pnma) as η-Ta2N3. Nb2N3 consists of regular-shaped polyhedra, and the bulk modulus has been determined to K0 = 300(2) GPa. The low-temperature X-ray diffraction measurements have been successfully conducted for the tiny novel Nb2N3 between 297.7(5) and 106.3(3) K under ambient pressure. Nb2N3 shows no structural phase transition down to 106.3(3) K, and investigation of the linear thermal expansion coefficients yields αa = 3.36(9) × 10-6 K-1, αb = 5.39(10) × 10-6 K-1, αc = 6.77(15) × 10-6 K-1, respectively. Our study reveals that the incompressible novel nitride shows low thermal expansion behavior, which offers new insights for the development of functional nitrides and their crystal chemistry.

International journal of ceramic engineering & science 2(2), 76 - 82 (2020). doi:10.1002/ces2.10036, Transparent nanoceramics, synthesized at extreme conditions of high pressure and temperature, are new classes of materials highly attractive for photonic applications, such as optical windows, which require additional increased hardness and toughness. In this study, mechanical properties of transparent polycrystalline nanoceramics consisting of triclinic Al$_2$SiO$_5$ kyanite (~91.4 vol%) and trigonal Al$_2$O$_3$ corundum (~8.6 vol%) fabricated at high pressure (10 GPa) and temperature (1200‐1400°C) were investigated. It is already known that the optical transparency of kyanite‐based nanoceramics increases with decreasing average grain size. The present study shows that the hardness of these ceramics increases with decreasing grain sizes down to ~70 nm according to the Hall‐Petch strengthening. This grain size seems to mark a transition range where an inverse Hall‐Petch effect is indicated due to signs of a moderate hardness decrease at a smaller grain size of ~35 nm. The observed hardness‐grain size relation can fairly be described by an existing composite model, which considers the crystals to be harder than the noncrystalline grain boundaries. Within the range of average grain sizes examined, the kyanite habit changes from more equant to more columnar. This behavior is associated with the observed strong crack deflection by the columnar kyanite grains with aspect (length to diameter) ratios ranging from ~2 to 10 and may positively affect the fracture toughness., Published by Wiley, Hoboken, NJ

Tungsten nitride continues to drive fundamental interests because of its potential as a functional compound, which combines features such as high hardness together with thermal, chemical, and wear resistance. Here, we report a novel tungsten nitride phase synthesized from MoC-type WN

X-ray diffraction and Raman scattering measurements, and first-principles calculations are performed to search for the formation of NaCl-hydrogen compound. When NaCl and H$_{2}$ mixture is laser-heated to above 1500 K at pressures exceeding 40 GPa, we observed the formation of NaClH$_{\textit{x}}$ with $\textit{P}$6$_{3}$/$\textit{mmc}$ structure which accommodates H$_{2}$ molecules in the interstitial sites of NaCl lattice forming ABAC stacking. Upon the decrease of pressure at 300 K, NaClH$_\textit{x}$ remains stable down to 17 GPa. Our calculations suggest the observed NaClH$_{\textit{x}}$ is NaCl(H$_{2}$). Besides, a hydrogen-richer phase NaCl(H$_{2}$)$_{4}$ is predicted to become stable at pressures above 40 GPa.

Lithium ionic conductivities of two LiBO2 polymorphs, i.e. the same composition Li borates: α-LiBO2 and γ-LiBO2, which are ambient and high-pressure phases, have been measured by the AC impedance method between 450 and 520 K using their high-density polycrystalline samples synthesized under high pressures. It is found the intra-grain and total conductivities of the γ-LiBO2 have been measured for the first time and be of the order 10−5 ∼ 10−6 Scm−1 and 10−6 Scm−1, respectively, both of which are higher in whole measured temperature range than those of the α-LiBO2. The higher lithium ionic conductivities of the former are discussed from the viewpoints of local structure and Li ion network in the crystal structures of the α-LiBO2 and γ-LiBO2.

The electronic structures of platinum-group metal pernitrides MN2 (M = Ru, Rh, Ir, and Pt) were investigated via synchrotron radiation infrared spectroscopy and first-principles calculations. Measured reflectance spectra of marcasite-type RuN2 and RhN2 showed Drude-like responses, approaching 1 as the photon energy was decreased, whereas reflectance of arsenopyrite-type IrN2 and pyrite-type PtN2 became ∼0.3 in the low photon energy region with a few features. These findings agreed well with the predictions of the metallic nature of marcasite-type RuN2 and RhN2 and the semiconducting properties of arsenopyrite-type IrN2 and pyrite-type PtN2, respectively. The measured reflectance spectra were also reasonably consistent with the calculated optical responses. The band gaps of IrN2 and PtN2 were estimated to be 0.8 and 2.1 eV, respectively, via first-principles calculation with a modified Becke–Johnson (MBJ) potential for the exchange potential., ファイル公開：2021-04-01

A novel niobium nitride, U

The high-pressure behavior of Li7La3Zr2O12 (LLZO) with a garnet-related structure has been investigated for the first time by high pressure in situ X-ray diffraction measurements and Raman spectroscopy using a diamond anvil cell. It was found that the tetragonal LLZO transforms to the high-pressure cubic phase (HP-c-LLZO) at 71.8 GPa in a N2 medium and at 25.8 GPa in the absence of pressure mediums. Uniaxial compression in the absence of pressure mediums induced the phase transition at much lower pressures than in the hydrostatic case when N2 was used as the pressure medium. High pressure in situ Raman spectroscopy suggested that the Li coordination in HP-c-LLZO was different from that reported in cubic LLZO, which had been stabilized by doping Al at ambient pressure and room temperature.

A novel Cr 3 C 2 -Ni cermets were successfully in-situ synthesized with Cr, C and Ni (20 wt%) mixed-powder at 1100 °C under 0–6 GPa isostatic pressure using a small-sized cubic-type multi-anvil press apparatus. High purity Cr 3 C 2 phase was generated in the cermets. Comparing with the conventional and reactive sintering, the sintering temperature and the average grain size of Cr 3 C 2 decreased by 200 °C and 50%, respectively. The physical properties, normalized lattice parameters and volumes of Cr 3 C 2 −20 wt%Ni cermet as a function of pressure had been studied both experimentally and by first-principles calculations for the first time.

A new structural polymorph of Li3BP2O8 has been successfully synthesized via a solid-state reaction between Li3PO4 and BPO4 at 4 GPa and 600 °C. The high-pressure phase of Li3BP2O8 (HP-Li3BP2O8) was found to crystallize in monoclinic symmetry with the cell parameters of a = 8.57010(4) A, b = 11.11812(5) A, c = 5.55380(3) A, and β = 97.7269(3)° [space group P21/ a (No. 14)]. HP-Li3BP2O8 has a new crystal structure that has not been reported so far. The total ionic conductivities measured for the polycrystalline sample by alternating-currrent impedance were 3.4 × 10-7 and 2.1 × 10-6 S/cm at 399 and 456 K, respectively. The lithium ionic conductivity of HP-Li3BP2O8 was higher than that of the low-pressure phase Li3BP2O8 in the temperature range of 375-456 K. This is caused by the difference in the dimensions of the lithium arrangements between LP- and HP-Li3BP2O8.

The chemical reaction of group-14 elements with molecular nitrogen at pressures above 60 GPa successfully leads to the formation of pyrite-type pernitrides. These new crystalline group-14 elemental pernitrides were found to show a bulk modulus higher than the other known group-14 elemental nitrides. Our results offer significant new progress in the solid-state chemistry of nitrides.

Highly coordinated iron and cobalt nitrides were successfully synthesized via direct chemical reaction between a transition metal and molecular nitrogen at pressures above approximately 30 GPa using a laser-heated diamond anvil cell. The synthesized novel transition metal nitrides were found to crystallize into the NiAs-type or marcasite-type structure. NiAs-type FeN could be quenched at ambient pressure, although it was gradually converted to the ZnS-type structure after the pressure was released. On the other hand, CoN was recovered with ZnS-type structure through a phase transition from NiAs-type structure at approximately a few gigapascals during decompression. Marcasite-type CoN2 was also synthesized at pressures above approximately 30 GPa. High-pressure in situ X-ray diffraction measurement showed that the zero-pressure bulk modulus of marcasite-type CoN2 is 216(18) GPa, which is comparable to that of RhN2. This indicates that the interatomic distance of the N–N dimer in marcasite-type CoN2 is short...

A-site columnar-ordered double perovskites, LnMn(Ga0.5Ti0.5)2O6 (Ln = Sm, Gd), were successfully synthesized under high pressure and high temperature (6 GPa, 1375 K). From the synchrotron powder X-ray diffraction patterns, all of the diffraction peaks can be indexed by the P42/nmc space group with lattice parameters a, c ≈ 2ap (ap: primitive cubic perovskite lattice) and no ordering of the B-site cations. Rietveld analysis of the synchrotron powder X-ray diffraction patterns and Curie–Weiss fitting of their magnetizations reveal that the ionic formulae of these perovskites are Ln3+Mn2+(Ga3+0.5Ti4+0.5)2O2–6. SmMn(Ga0.5Ti0.5)2O6 shows canted-antiferromagnetic behavior, whereas GdMn(Ga0.5Ti0.5)2O6 exhibits two different magnetic states at low temperature depending on the applied magnetic field and shows an unusual magnetization curve. These magnetic behaviors originate by decreasing the antiferromagnetic interaction by substituting Ga3+(d10) for Ti4+(d0) and by decreasing the ferromagnetic interaction between columnar-ordered Ln3+ and Mn2+.

A hexagonal chromium pernitride, ${\mathrm{CrN}}_{2}$, has been successfully synthesized $via$ a direct chemical reaction between chromium and molecular nitrogen at a pressure of approximately 70 GPa. The advanced synchrotron x-ray diffraction (XRD) measurements after recovery and structural refinement at 0.1 MPa demonstrated that ${\mathrm{CrN}}_{2}$ crystallizes in the anti-NiAs-type structure with lattice parameters of $a=2.7465(3)\phantom{\rule{0.16em}{0ex}}\AA{}$ and $c=7.3670(4)\phantom{\rule{0.16em}{0ex}}\AA{}$. Micron-sized hexagonal habit compounds were found in the synthesized products, which indicated that the single crystal of hexagonal ${\mathrm{CrN}}_{2}$ was grown in the supercritical nitrogen at high pressure. High-pressure in situ XRD measurements were performed to determine the zero-pressure bulk modulus, ${K}_{0}$, value of 286(6) GPa $[{{K}^{\ensuremath{'}}}_{0}=2.5(7)]$ and remarkable incompressibility of the $c$ axis. ${\mathrm{CrN}}_{2}$ is a unique example of the recoverable transition-metal pernitride which presents one-dimensionally aligned N-N dimers in the structure. The one-dimensionally aligned N-N dimers play an important role in controlling the mechanical and electronic properties of ${\mathrm{CrN}}_{2}$ as predicted by theoretical calculations.

A new structural polymorph of Li

The electronic structure of newly synthesized marcasite-type cobalt pernitride (CoN2) is investigated using X-ray absorption and photoelectron spectroscopy (XAS and XPS), in combination with the el...

Within the exploration of sustainable and functional materials, narrow bandgap magnesium silicide semiconductors have gained growing interest. Intriguingly, squeezing silicides to extreme pressures and exposing them to non-ambient temperatures proves fruitful to study the structural behavior, tune the electronic structure, or discover novel phases. Herein, structural changes and thermoelastic characteristics of magnesium silicides were probed with synchrotron x-ray diffraction techniques using the laser-heated diamond anvil cell and large volume press at high pressure and temperature and temperature-dependent synchrotron powder diffraction. Probing the ambient phase of Mg2Si (anti-CaF2-type Mg2Si, space group: Fm3¯m) at static pressures of giga-Pascals possibly unveiled the transformation to metastable orthorhombic anti-PbCl2-type Mg2Si (Pnma). Interestingly, heating under pressures introduced the decomposition of Mg2Si to hexagonal Mg9Si5 (P63) and minor Mg. Using equations of state (EoS), which relate pressure to volume, the bulk moduli of anti-CaF2-type Mg2Si, anti-PbCl2-type Mg2Si, and Mg9Si5 were determined to be B0 = 47(2) GPa, B0 ≈ 72(5) GPa, and B0 = 58(3) GPa, respectively. Employing a high-temperature EoS to the P–V–T data of anti-CaF2-type Mg2Si provided its thermoelastic parameters: BT0 = 46(3) GPa, B′T0 = 6.1(8), and (∂BT0/∂T)P = −0.013(4) GPa K−1. At atmospheric pressure, anti-CaF2-type Mg2Si kept stable at T = 133–723 K, whereas Mg9Si5 transformed to anti-CaF2-type Mg2Si and Si above T ≥ 530 K. This temperature stability may indicate the potential of Mg9Si5 as a mid-temperature thermoelectric material, as suggested from previous first-principles calculations. Within this realm, thermal models were applied, yielding thermal expansion coefficients of both silicides together with estimations of their Gruneisen parameter and Debye temperature.

The synthesis of multicomponent perovskites (Ln0.25Mn0.75)(Al0.25Ti0.75)O3 (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Y) have been investigated using a high-pressure and high-temperature (6 GPa, 1175 °C) technique. When Ln3+ is larger La3+, Pr3+, Nd3+, the A-site ordered perovskites, LnMn3(Al0.25Ti0.75)4O12 in Im-3, have been successfully synthesized. The A-site partially disordered one, (Sm0.80Mn0.20)(Sm0.07Mn0.93)3(Al0.25Ti0.75)4O12 is also obtained. In the case of smaller Gd3+, Tb3+, Dy3+, we have obtained no single phase but two decomposed perovskite phases. When Ln3+ is much smaller Y3+, it is crystallized as an A-site disorder one in Pnma. The Rietveld structural refinements of the A-site ordered and partially disordered perovskites indicate that the tilting of (Al/Ti)O6 octahedrons for the A-site ions ordering is correlated with the (Al/Ti)–O and Ln–O bond lengths to optimize the coordination of the A- and A′-sites. The phase stability of the A-site ordered perovskites is discussed from the viewpoint of this correlation.

A new multicomponent A-site ordered perovskite-type oxide has been successfully synthesized in the BiFeO 3 and MnTiO 3 pseudobinary system at high pressure and temperature, 6 GPa and 1300 K. It is found that the oxide is an A-site ordered and B-site disordered perovskite Bi 3+ Mn 2+ 3 (Fe 3+ 0.25 Ti 4+ 0.75 ) 4 O 12 in the space group of the cubic high symmetry Im -3 with a lattice parameter a =7.5937(3) A. It should be noted that the Mn 2+ ions in the A ′-site show a site-splitting, while the Bi 3+ ones are in a regular icosahedron position of the A -site. On the other hand, the Fe 3+ and Ti 4+ ones in the B -site are disordered in this perovskite structure. The temperature dependence of magnetizations and specific heats at low temperatures shows spin-glass-like behaviors below 11 K.

Nanowire crystals of a tantalum nitride phase have been grown from epsilon-tantalum nitride and ammonium halide precursors at high pressures exceeding several gigapascals. Synchrotron x-ray diffraction and Transmission Electron Microscopy (TEM) observations revealed that they had crystallized in an unreported hexagonal structure with lattice parameters of a = 3.050(1) Å and c = 2.909(2) Å. The one-dimensional growth orientation was along the crystallographic [001] direction. Scanning TEM–EDX elemental analyses showed that the nanowire crystals were composed of tantalum and nitrogen with small amounts of oxygen. The presence of the melted ammonium halides combined with supercritical ammonia acting as a reactive flux at high pressure and temperature played a significant role in the nanowire crystal growth. Raman spectroscopy performed on several single crystal nanowires pointed toward metallic properties, and the temperature dependence of the magnetization measured by Superconducting Quantum Interference Device magnetometry suggested a superconducting transition about 6.2 K. The analysis of the compression behavior revealed an incompressible nature, and the bulk modulus was determined to be 363(6) GPa., ファイル公開：2021/03/24

Nb hydrides formation in 10-GPa supercritical water has been investigated by angle-dependent micro-beam hard X-ray photoemission spectroscopy. In the Nb 3d core-level spectra, Nb hydride components are found in the slightly high binding energy side of the metallic components, and the oxide ones are observed even though little oxides are recognized in X-ray diffraction patterns. Obtained emission-angle dependence of the Nb 3d core-level spectra of Nb hydride specimens shows that the Nb hydride components increase with the emission angle decreased i.e. the sampling depth increased, while the oxide ones decrease. The bulk valence-band spectrum is obtained by decomposing the measured valence-band spectra into a bulk and surface components with use of the emission-angle dependence of the core-level and valence-band spectra; it consists of two bands. This implies the Nb–H chemical bond formation and Nb in an oxidation state, consistent with reported band structure calculations and the observed core-level chemical shifts. Thus it is confirmed by valence-band and core-level photoelectron spectroscopy that the Nb hydrides are formed inside the specimen, irrespective to the well-known high oxidation ability of supercritical water.

BaTiO3–SnO solid solutions have been investigated from the viewpoints of synthesis and Sn ion valence. First-principles calculations show that the solution energy of Sn2+ into the Ba sites in BaTiO3 is less than that into the Ti sites under high pressure. The BaTiO3–SnO solid solutions have been synthesized under high pressure (∼20 GPa) and temperatures using a laser-heated diamond anvil cell. The synthesized materials have been characterized using x-ray diffractometry, scanning transmission electron microscopy, and energy-dispersive x-ray spectroscopy. It is found from these various methods that we have successfully synthesized uniform solid solutions of BaTiO3–SnO. Furthermore, it is also clarified by the Sn L3-edge electron energy loss spectra measurements that the valences of the Sn ions in the BaTiO3–SnO solid solution are 2+. These results indicate that the Sn2+ ions are substituted into the Ba sites, according to the ion size. Consequently, the Sn ions can be substituted into the Ba sites of the shrinking BaTiO3 lattice under high pressure, which is similar to the Ca and Sn co-substitution into Ba sites under ambient pressure as reported previously.

The last remaining marcasite-type RuN2 was successfully synthesized by direct chemical reaction between ruthenium and molecular nitrogen above the pressure of 32 GPa. For the first time, we found that Ru 4d is weakly hybridized with N 2p in the structure by using transmission electron microscopy equipped with electron-energy-loss spectroscopy. Our finding give important knowledge about the platinum-group pernitride with respect to the chemical bonding between platinum-group element and nitrogen.

High-pressure behaviors of Linde-type A (LTA) zeolite were investigated using a quasi-hydrostatic pressure medium of noble gases (helium or argon). High-pressure in situ X-ray diffraction measurements combined with the use of a diamond anvil cell did not observe any structural phase transition for LTA zeolites up to a pressure of approximately 12 GPa at room temperature. However, it was found that the compressibility strongly depended not only on the pressure medium but also on the pressurization process. LTA zeolites showed significant incompressible behaviors at pressures between 2 and ∼7 GPa when it was compressed in helium. Based on careful analyses of the data together with the results of previous high-pressure studies, the incompressibility of LTA zeolites was induced by the penetration of a large amount of noble gas atoms into the cages of LTA zeolites under high pressures. The present results offer interesting and important information on the atomic diffusion process for open-structured materials under high pressures and thus have great implications for the development of new noble-gas-atom filled materials, as well as geochemical implications.

We have characterized Nb hydrides synthesized in high-pressure supercritical water by hard X-ray photoelectron spectroscopy. Comparison is made, in particular, of the Nb 2p core level spectra and valence band ones for the Nb hydride specimens in different stages of hydrogenation with those for Nb oxide and metallic references. The Nb 2p core level spectra of the Nb hydride specimens synthesized at relatively low temperature show an intense Nb 2 O 5 component and a shoulder structure, which is attributed to Nb hydrides, at the high binding energy side of a metallic component of the Nb metal. The valence band spectra of the Nb hydride specimens also show a broad band at the binding energy E B between 5 and 9 eV, which is ascribed mainly to Nb oxides. The present results indicate that the surface of the synthesized Nb hydrides is covered with several 10 nm thick Nb oxides and suggest that the Nb hydrides are formed deep inside the specimens. The Nb 2p chemical shift implies the Nb valence of +1.4 for the synthesized hydride NbH x .

We have measured the solubility of argon in SiO2 melt under high pressure by melting a SiO2 crystal at the argon pressure as high as 19 GPa using laser-heated diamond anvil cell (LHDAC). SiO2 was successfully melted at the pressure of about 12 GPa and recovered with a completely glassy phase. Above 15 GPa, the sample contained a large amount of crystalline SiO2, although it was completely melted and spherical due to the surface tension. This may arise from the change in the coordination number of Si in SiO2 melt at around 12–15 GPa, which is close to the triple point of coesite, stishovite, and liquid SiO2. Argon content in the recovered SiO2 was measured by energy-dispersive spectroscopy and mass spectrometry. It increased at pressures up to approximately 5–7 GPa and exhibited a constant value up to at least 12 GPa; this implies that, at these conditions, the noble gas behaves as an incompatible element. The result is completely different from those of previous LHDAC studies, which claimed that the increased solubility then dramatically drops above the pressure of about 5 GPa. Here, we report the new details of experimentally determined pressure dependence of noble gas solubility by LHDAC, and discuss the experimental difficulties and the structure change of silicate melt under high pressures.

The perovskite (Pv) to post-perovskite (PPv) phase transition and the deformation texture of the PPv phase were investigated on the basis of a high-pressure X-ray diffraction (XRD) study of CaIrO3 using a diamond-anvil cell in a pressure range up to 31 GPa. The development of a crystallographic preferred orientation (CPO) in the PPv phase was observed after the plastic deformation from 8 or 9 GPa to 31 GPa at both room and high (∼1500 K) temperatures. The observed CPOs in the present study indicate that the (0 1 0) plane worked as an active slip plane in the PPv phase over the entire pressure and temperature range of the present experiment. We also confirmed that the Pv to PPv phase transition proceeds at room temperature under high-stress conditions. The phase transition under high-stress condition is in stark contrast to the results of a previous hydrostatic experiment in which the Pv-CaIrO3 remained stable in a helium media at 31 GPa and room temperature. This indicates that shear stress plays an important role in the Pv to PPv phase transition, and this effect should be taken into account when the thermal structure at the D″ layer is discussed on the basis of the high-pressure experiments.

Structures of 3-­isopropylmalate dehydrogenase were determined at pressures ranging from 0.1 to 650 MPa. Comparison of these structures gives a detailed picture of the swelling of a cavity at the dimer interface and the generation of a new cleft on the molecular surface, which are accompanied by water penetration., Hydrostatic pressure induces structural changes in proteins, including denaturation, the mechanism of which has been attributed to water penetration into the protein interior. In this study, structures of 3-isopropylmalate dehydrogenase (IPMDH) from Shewanella oneidensis MR-1 were determined at about 2 Å resolution under pressures ranging from 0.1 to 650 MPa using a diamond anvil cell (DAC). Although most of the protein cavities are monotonically compressed as the pressure increases, the volume of one particular cavity at the dimer interface increases at pressures over 340 MPa. In parallel with this volume increase, water penetration into the cavity could be observed at pressures over 410 MPa. In addition, the generation of a new cleft on the molecular surface accompanied by water penetration could also be observed at pressures over 580 MPa. These water-penetration phenomena are considered to be initial steps in the pressure-denaturation process of IPMDH.

The rock salt (B1) structure of binary oxides or chalcogenides transforms to the CsCl (B2) structure under high pressure, with critical pressures P(s) depending on the cation to anion size ratio (R(c)/R(a)). We investigated structural changes of A(2)MO(3) (A = Sr, Ca; M = Cu, Pd) comprising alternate 7-fold B1 AO blocks and corner-shared MO(2) square-planar chains under pressure. All of the examined compounds exhibit a structural transition at P(s) = 29-41 GPa involving a change in the A-site geometry to an 8-fold B2 coordination. This observation demonstrates, together with the high pressure study on the structurally related Sr(3)Fe(2)O(5), that the B1-to-B2 transition generally occurs in these intergrowth structures. An empirical relation of P(s) and the R(c)/R(a) ratio for the binary system holds well for the intergrowth structure also, which means that P(s) is predominantly determined by the rock salt blocks. However, a large deviation from the relation is found in LaSrNiO(3.4), where oxygen atoms partially occupy the apical site of the MO(4) square plane. We predict furthermore the occurrence of the same structural transition for Ruddlesden-Popper-type layered perovskite oxides (AO)(AMO(3))(n), under higher pressures. For investigating the effect on the physical properties, an electrical resistivity of Sr(2)CuO(3) is studied.

Rectangular hollow tube crystals of the rutile-type TiO2 have been successfully grown in supercritical water at about 2 GPa for the first time using a diamond-anvil cell combined with the infrared laser heating system. The scanning electron microscope (SEM) and transmission electron microscope (TEM) observations indicate that they are grown along the [001] direction in a few tens of micrometer lengths. It is also found that they are surrounded by the {110} face with its wall thickness of ∼200 nm. Details of the morphology, optical property, and growth mechanism of the obtained crystals are discussed.

Marcasite-type rhodium nitride was successfully synthesized in a direct chemical reaction between a rhodium metal and molecular nitrogen at 43.2 GPa using a laser-heated diamond-anvil cell. This material shows a low zero-pressure bulk modulus of K0 = 235(13) GPa, which is much lower than those of other platinum group nitrides. This finding is due to the weaker bonding interaction between metal atoms and quasi-molecular dinitrogen units in the marcasite-type structure, as proposed by theoretical studies.

Compression behaviors of CaIrO3 with perovskite (Pv) and post-perovskite (pPv) structures have been investigated up to 31.0(1.0) and 35.3(1) GPa at room temperature, respectively, in a diamond-anvil cell with hydrostatic pressure media. CaIrO3 Pv and pPv phases were compressed with the axial compressibility of β a > β c > β b and β b > β a > β c, respectively and no phase transition was observed in both phases up to the highest pressure in the present study. The order of axial compressibility for pPv phase is consistent with the crystallographic consideration for layer structured materials and previous experimental results. On the other hand, Pv phase shows anomalous compression behavior in b axis, which exhibit constant or slightly expanded above 13 GPa, although the applied pressure remained hydrostatic. Volume difference between Pv and pPv phases was gradually decreased with increasing pressure and this is consistent with the results of theoretical study based on the ab initio calculation. Present results, combined with theoretical study, suggest that these complicate compression behaviors in CaIrO3 under high pressure might be caused by the partially filled electron of Ir4+. Special attention must be paid in case of using CaIrO3 as analog materials to MgSiO3, although CaIrO3 exhibits interesting physical properties under high pressure.

Lattice-preferred orientations (LPOs) of post-perovskite (PPv)-type MgGeO 3 formed by transformations from two different pre-phases, orthopyroxene (OPx) and perovskite (Pv), were studied using radial and axial X-ray diffraction techniques combined with a laser-heated diamond-anvil cell. When the PPv was made from Pv, strong LPO was formed in the PPv immediately after the transformation with an alignment of the (0 0 1) or (0 1 1) plane almost perpendicular to the compression axis. This present result contrasts markedly from that observed when the PPv was formed from OPx and those reported on MgGeO 3 -PPv and (Mg,Fe)SiO 3 -PPv transformed from OPx, in which the (1 0 0) or (1 1 0) plane was aligned to the compression axis. It was clarified that when the PPv-type MgGeO 3 is formed in diamond-anvil cells, it has strong transformation-induced LPO from the beginning even before plastic deformation occurs, and that its characteristics depend on the pre-phase before the transformation. The formed transformation-induced LPO of PPv did not change in spite of further compression using a conventional gasket because the sample became too thin to deform. However, by using a diamond gasket technique, we were able to deform the PPv at room temperature, resulting in significant variations of the relative intensities of several diffraction peaks. The change in the axial diffraction patterns can be explained only by assuming that the (0 0 1) plane aligns almost perpendicularly to the compression axis. The present results suggest that the (0 0 1) is a dominant slip plane in MgGeO 3 -PPv at room temperature. If one makes the assumption that the dominant slip system(s) of silicate PPv deformed in the D″ layer is or are identical to that of germanate PPv at room temperature, then a large S-wave polarization anisotropy in the Earth's D″ layer would be explained by the small degree of deformation-induced LPO of the PPv phase that is expected to exist in this layer.

Single crystals of rutile-type GeO 2 having a structure equivalent to that of TiO 2 , a well-known photocatalyst, have been grown for the first time in supercritical oxygen at approximately 5 GPa and 3000 K. The obtained crystals exhibit a rectangular hollow tube structure with submicron size (cross section with sides of ∼500 nm, wall thickness of ∼20 nm, and longitudinal length of ∼5 μm). These single crystals were grown within 1 s and along the c -axis surrounded by the (1 1 0) faces. The crystal growth mechanism strongly depends on the growth mechanism of rutile-type oxides, and the extremely short growing time is an important factor in the formation of hollow tube crystals.

This paper reports a procedure to combine the focused ion beam micro-sampling method with conventional Ar-milling to prepare high-quality site-specific transmission electron microscopy cross-section samples. The advantage is to enable chemical and structural evaluations of oxygen dissolved in a molten iron sample to be made after quenching and recovery from high-pressure experiments in a laser-heated diamond anvil cell. The evaluations were performed by using electron energy-loss spectroscopy and high-resolution transmission electron microscopy. The high signal to noise ratios of electron energy-loss spectroscopy core-loss spectra from the transmission electron microscopy thin foil, re-thinned down to 40 nm in thickness by conventional Argon ion milling, provided us with oxygen quantitative analyses of the quenched molten iron phase. In addition, we could obtain lattice-fringe images using high-resolution transmission electron microscopy. The electron energy-loss spectroscopy analysis of oxygen in Fe(0.94)O has been carried out with a relative accuracy of 2%, using an analytical procedure proposed for foils thinner than 80 nm. Oxygen K-edge energy-loss near-edge structure also allows us to identify the specific phase that results from quenching and its electronic structure by the technique of fingerprinting of the spectrum with reference spectra in the Fe-O system.