Polymorphs of the Gadolinite-Type Borates ZrB2 O5 and HfB2 O5 Under Extreme Pressure.

Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO4 (OH), the behavior of the isostructural borates ß-HfB2 O5 and ß-ZrB2 O5 have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB2 O5 features a rearrangement of the corner-sharing BO4 tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB2 O5 contains ten-membered rings including the rare structural motif of edge-sharing BO4 tetrahedra with exceptionally short B-O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf4+ , and tenfold coordinated Zr4+ , respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs.

High-Pressure Synthesis of the ß-Zn3N2 Nitride and the α-ZnN4 and ß-ZnN4 Polynitrogen Compounds.

High-pressure nitrogen chemistry has expanded at a formidable rate over the past decade, unveiling the chemical richness of nitrogen. Here, the Zn-N system is investigated in laser-heated diamond anvil cells by synchrotron powder and single-crystal X-ray diffraction, revealing three hitherto unobserved nitrogen compounds: ß-Zn3N2, α-ZnN4, and ß-ZnN4, formed at 35.0, 63.5, and 81.7 GPa, respectively. Whereas ß-Zn3N2 contains the N3- nitride, both ZnN4 solids are found to be composed of polyacetylene-like [N4]∞2- chains. Upon the decompression of ß-ZnN4 below 72.7 GPa, a first-order displacive phase transition is observed from ß-ZnN4 to α-ZnN4. The α-ZnN4 phase is detected down to 11.0 GPa, at lower pressures decomposing into the known α-Zn3N2 (space group Ia3̅) and N2. The equations of states of ß-ZnN4 and α-ZnN4 are also determined, and their bulk moduli are found to be K0 = 126(9) GPa and K0 = 76(12) GPa, respectively. Density functional theory calculations were also performed and provide further insight into the Zn-N system. Moreover, comparing the Mg-N and Zn-N systems underlines the importance of minute chemical differences between metal cations in the resulting synthesized phases.

A Room-Temperature Verwey-type Transition in Iron Oxide, Fe5 O6.

Functional oxides whose physicochemical properties may be reversibly changed at standard conditions are potential candidates for the use in next-generation nanoelectronic devices. To date, vanadium dioxide (VO2 ) is the only known simple transition-metal oxide that demonstrates a near-room-temperature metal-insulator transition that may be used in such appliances. In this work, we synthesized and investigated the crystals of a novel mixed-valent iron oxide with an unconventional Fe5 O6 stoichiometry. Near 275 K, Fe5 O6 undergoes a Verwey-type charge-ordering transition that is concurrent with a dimerization in the iron chains and a following formation of new Fe-Fe chemical bonds. This unique feature highlights Fe5 O6 as a promising candidate for the use in innovative applications. We established that the minimal Fe-Fe distance in the octahedral chains is a key parameter that determines the type and temperature of charge ordering. This model provides new insights into charge-ordering phenomena in transition-metal oxides in general.

Experimental evidence of superionic conduction in H2O ice.

Ionic conductivity and molar volume measurements were performed on H(2)O ice at high pressure (P) and temperature (T) in a resistive-heated diamond anvil cell. The conductivity data obtained at P = 20-62 GPa, T = 304-930 K are well fitted with a single Arrhenius equation. Isothermal volume measurements at T = 873 K, P = 30-101 GPa indicate that H(2)O ice undergoes phase transitions at P = 50 GPa and 53 GPa due to hydrogen-bond symmetrization. Combining these results, we suggest that the conduction mechanism does not change with pressure-induced hydrogen-bond symmetrization. Along the Arrhenius behavior of conductivity data, the experimental evidence for superionic conduction (>10(-1) S/cm) was found at T = 739 K, P = 56 GPa and T = 749 K, P = 62 GPa, which is significantly low temperature compared with earlier theoretical estimates resorted to the observation of a drastic rise of the melting curve. We infer that the sudden increase of the melting temperature is not related to the onset of superionic conduction, but is attributed to the phase change regarding to the symmetrization.

Face-Centered Cubic Refractory Alloys Prepared from Single-Source Precursors.

Three binary fcc-structured alloys (fcc-Ir0.50Pt0.50, fcc-Rh0.66Pt0.33 and fcc-Rh0.50Pd0.50) were prepared from [Ir(NH3)5Cl][PtCl6], [Ir(NH3)5Cl][PtBr6], [Rh(NH3)5Cl]2[PtCl6]Cl2 and [Rh(NH3)5Cl][PdCl4]·H2O, respectively, as single-source precursors. All alloys were prepared by thermal decomposition in gaseous hydrogen flow below 800 °C. Fcc-Ir0.50Pt0.50 and fcc-Rh0.50Pd0.50 correspond to miscibility gaps on binary metallic phase diagrams and can be considered as metastable alloys. Detailed comparison of [Ir(NH3)5Cl][PtCl6] and [Ir(NH3)5Cl][PtBr6] crystal structures suggests that two isoformular salts are not isostructural. In [Ir(NH3)5Cl][PtBr6], specific Br…Br interactions are responsible for a crystal structure arrangement. Room temperature compressibility of fcc-Ir0.50Pt0.50, fcc-Rh0.66Pt0.33 and fcc-Rh0.50Pd0.50 has been investigated up to 50 GPa in diamond anvil cells. All investigated fcc-structured binary alloys are stable under compression. Atomic volumes and bulk moduli show good agreement with ideal solutions model. For fcc-Ir0.50Pt0.50, V0/Z = 14.597(6) Å3·atom-1, B0 = 321(6) GPa and B0' = 6(1); for fcc-Rh0.66Pt0.33, V0/Z = 14.211(3) Å3·atom-1, B0 =259(1) GPa and B0' = 6.66(9) and for fcc-Rh0.50Pd0.50, V0/Z = 14.18(2) Å3·atom-1, B0 =223(4) GPa and B0' = 5.0(3).

Raman Spectroscopy Study on Chemical Transformations of Propane at High Temperatures and High Pressures.

This study is devoted to the detailed in situ Raman spectroscopy investigation of propane C3H8 in laser-heated diamond anvil cells in the range of pressures from 3 to 22 GPa and temperatures from 900 to 3000 K. We show that propane, while being exposed to particular thermobaric conditions, could react, leading to the formation of hydrocarbons, both saturated and unsaturated as well as soot. Our results suggest that propane could be a precursor of heavy hydrocarbons and will produce more than just sooty material when subjected to extreme conditions. These results could clarify the issue of the presence of heavy hydrocarbons in the Earth's upper mantle.

High pressure phase transitions of paracelsian BaAl2Si2O8.

Three new polymorphs of aluminosilicate paracelsian, BaAl2Si2O8, have been discovered using synchrotron-based in situ high-pressure single crystal X-ray diffraction. The first isosymmetric phase transition (from paracelsian-I to paracelsian-II) occurs between 3 and 6 GPa. The phase transition is associated with the formation of pentacoordinated Al3+ and Si4+ ions, which occurs in a stepwise fashion by sequential formation of Al-O and Si-O bonds additional to those in AlO4 and SiO4 tetrahedra, respectively. The next phase transition occurs between 25 and 28 GPa and is accompanied by the symmetry change from monoclinic (P21/c) to orthorhombic (Pna21). The structure of paracelsian-III consists of SiO6 octahedra, AlO6 octahedra and distorted AlO4 tetrahedra, i.e. the transition is reconstructive and associated with the changes of Si4+ and Al3+ coordination, which show rather complex behaviour with the general tendency towards increasing coordination numbers. The third phase transition is observed between 28 and 32 GPa and results in the symmetry decreasing from Pna21 to Pn. The transition has a displacive character. In the course of the phase transformation pathway up to 32 GPa, the structure of polymorphs becomes denser: paracelsian-II is based upon elements of cubic and hexagonal close-packing arrangements of large O2- and Ba2+ ions, whereas, in the crystal structure of paracelsian-III and IV, this arrangement corresponds to 9-layer closest-packing with the layer sequence ABACACBCB.

Pressure tuning of charge ordering in iron oxide.

A Verwey-type charge-ordering transition in magnetite at 120 K leads to the formation of linear units of three iron ions with one shared electron, called trimerons. The recently-discovered iron pentoxide (Fe4O5) comprising mixed-valent iron cations at octahedral chains, demonstrates another unusual charge-ordering transition at 150 K involving competing formation of iron trimerons and dimerons. Here, we experimentally show that applied pressure can tune the charge-ordering pattern in Fe4O5 and strongly affect the ordering temperature. We report two charge-ordered phases, the first of which may comprise both dimeron and trimeron units, whereas, the second exhibits an overall dimerization involving both the octahedral and trigonal-prismatic chains of iron in the crystal structure. We link the dramatic change in the charge-ordering pattern in the second phase to redistribution of electrons between the octahedral and prismatic iron chains, and propose that the average oxidation state of the iron cations can pre-determine a charge-ordering pattern.

Charge-ordering transition in iron oxide Fe4O5 involving competing dimer and trimer formation.

Phase transitions that occur in materials, driven, for instance, by changes in temperature or pressure, can dramatically change the materials' properties. Discovering new types of transitions and understanding their mechanisms is important not only from a fundamental perspective, but also for practical applications. Here we investigate a recently discovered Fe4O5 that adopts an orthorhombic CaFe3O5-type crystal structure that features linear chains of Fe ions. On cooling below ∼150 K, Fe4O5 undergoes an unusual charge-ordering transition that involves competing dimeric and trimeric ordering within the chains of Fe ions. This transition is concurrent with a significant increase in electrical resistivity. Magnetic-susceptibility measurements and neutron diffraction establish the formation of a collinear antiferromagnetic order above room temperature and a spin canting at 85 K that gives rise to spontaneous magnetization. We discuss possible mechanisms of this transition and compare it with the trimeronic charge ordering observed in magnetite below the Verwey transition temperature.

The Pressure-Induced Polymorphic Transformations in Fluconazole.

The structural properties and Raman spectra of fluconazole have been studied by means of X-ray diffraction and Raman spectroscopy at pressures up to 2.5 and 5.5 GPa, respectively. At a pressure of 0.8 GPa, a polymorphic phase transition from the initial form I to a new triclinic form VIII has been observed. At higher pressure of P = 3.2 GPa, possible transformation into another new polymorphic form IX has been detected. The unit cell parameters and volumes, and vibration modes as functions of pressure have been obtained for the different forms of fluconazole.

The polymorphic phase transformations in the chlorpropamide under pressure.

The crystal structure and vibrational spectra of the chlorpropamide have been studied by means of the X-ray diffraction and Raman spectroscopy at pressures up to 24.6 and 4.4 GPa, respectively. Two polymorphic phase transitions, between initial orthorhombic form-A and a monoclinic form-AI at P ∼ 1.2 GPa and, in additional, to another monoclinic form-AII at P ∼ 3.0 GPa, were observed. At pressures above 9.6 GPa, a transformation to the amorphous phase of chlorpropamide was revealed. The lattice parameters, unit cell volumes, and vibration modes as functions of pressure were obtained for the different polymorphic modifications of chlorpropamide.

The S3- ion is stable in geological fluids at elevated temperatures and pressures.

The chemical speciation of sulfur in geological fluids is a controlling factor in a number of processes on Earth. The two major chemical forms of sulfur in crustal fluids over a wide range of temperature and pressure are believed to be sulfate and sulfide; however, we use in situ Raman spectroscopy to show that the dominant stable form of sulfur in aqueous solution above 250°C and 0.5 gigapascal is the trisulfur ion S(3)(-). The large stability range of S(3)(-) enables efficient transport and concentration of sulfur and gold by geological fluids in deep metamorphic and subduction-zone settings. Furthermore, the formation of S(3)(-) requires a revision of sulfur isotope-fractionation models between sulfides and sulfates in natural fluids.

Unusual compression behavior of anatase TiO2 nanocrystals.

The size-dependent stiffness variations in nanocrystalline anatase, a leading material for applications in photovoltaics, photocatalysis, photoelectrochromics, sensors, and optical coatings, were determined using in situ synchrotron x-ray diffraction and Raman scattering. An unusual, abrupt change in the compression curve at approximately 10 GPa and subtle breaks in the pressure shifts of the intense E(g) Raman band at approximately 10 and approximately 15 GPa have been correlated with approximately 2 A-scale disordering of nanocrystalline anatase structure that fully amorphizes under high compression.

Optical absorption and radiative thermal conductivity of silicate perovskite to 125 gigapascals.

Mantle convection and plate tectonics are driven by the heat flow from Earth's core to the surface. The radiative contribution to heat transport is usually assumed to be negligible. Here, we report the near-infrared and optical absorption spectra of silicate perovskite, the main constituent of the lower mantle, to 125 gigapascals. Silicate perovskite remains quite transparent up to the pressures at the core-mantle boundary. Estimates of radiative thermal conductivity derived from these spectra approach 10 watts meter(-1) kelvin(-1) at lowermost mantle conditions, implying that heat conduction is dominated by radiation. However, the increase in radiative conductivity with temperature (T) is less pronounced than expected from a T3 dependency.

Size-dependent pressure-induced amorphization in nanoscale TiO2.

We investigated the size-dependent high-pressure phase transition behavior of nanocrystalline anatase TiO2 with synchrotron x-ray diffraction and Raman spectroscopy to 45 GPa at ambient temperature. Pressure-induced amorphization results in a high-density amorphous (HDA) form when the starting crystallite size is < 10 mm. The HDA-TiO2 transforms to a low-density amorphous form at lower pressures. Harnessing the nanometer length scale thus provides a new window for experimental investigation of amorphization in poor glass formers and a synthesis route for new amorphous materials.

Pressure-induced magnetization in FeO: evidence from elasticity and Mössbauer spectroscopy.

The complete elastic tensor of Fe0.94O (wüstite) has been determined to 10 GPa using acoustic interferometry at GHz frequencies inside a diamond-anvil cell. The soft mode (C44) elastic constant of FeO is reduced by 20% over the experimental pressure range. An unusual discontinuity in the pressure derivatives of C11 and C12 at 4.7+/-0.2 GPa corresponds to the pressure at which the onset of a magnetic ordering transition is observed by high-pressure Mössbauer spectroscopy and neutron powder diffraction. Our new results combined with literature structural high P-T data suggest that there is a magnetic, although still cubic, phase of FeO between approximately 5 and approximately 17 GPa.