Structural transitions in hydrogen and deuterium at ultrahigh pressures

Abstract

Raman measurements indicate that normal hydrogen and deuterium compressed in a diamond-anvil cell at 77 K undergo phase transformations at 145 (±l5) GPa and 190 (±l20) GPa, respectively. The new observations reported for deuterium indicate that the transition in both isotopes is a structural change not associated with a simple rotational ordering mechanism. The possibility of a structural transition driven by band-gap closure is discussed.     

Viscosity of argon to 5 GPa and 673 K

A rolling-sphere technique has been used to measure shear viscosities of (supercritical) fluid argon in the diamond-anvil cell between the temperatures of 294 and 673 K, up to a maximum pressure of 5 GPa. At these pressures, the viscosities can be fit to a modified free-volume expression. A single correlation between reduced viscosity and reduced residual entropy is shown to give a good account of the current high pressure data, data at lower pressures and those for the sub-critical liquid.     

Laboratory set-up for X-ray diffraction at high pressures

We describe here a simple set-up for X-ray diffraction under high pressure using a diamond anvil cell employing a sealed tube. The set-up works in angular dispersive geometry and is built using rather common components that are available in a research laboratory. We show that using this set-up one can routinely acquire good-quality data for the determination of structural properties under pressure and the equations of state. Technical details are presented along with examples of experimental results for sodium chloride and LiV₂O₄.     

High pressure Raman study on the local structure of 1-ethyl-3-methylimidazolium tetrafluoroborate

We have investigated the pressure-induced Raman spectral changes of 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF₄]). We found that [emim][BF₄] did not crystallize up to 1.2 GPa. The Raman CH stretching spectra arising from the CH₃ groups of the ethyl-chain and the CH₃ group adjacent to the imidazolium-ring in [emim]⁺ cation largely changed against pressure. Moreover, the Raman intensity of the CH₂ (N) bending band arising from the alkyl-chain drastically changes with increasing pressure, but that of the imidazolium-ring in-plane bending band arising from the imidazolium-ring is independent of pressure. Our results show that the environment around the alkyl-chain of [emim][BF₄] is largely perturbed rather than that around the imidazolium-ring upon compression.     

Optical pressure sensors for high-pressure–high-temperature studies in a diamond anvil cell

We review the various optical pressure sensors that are suitable for high-pressure and high-temperature studies in a diamond anvil cell. Two different kinds of sensors are considered: those based on the pressure shift of a fluorescence line (ruby, SrB₄O₇:Sm²⁺) and those based on the pressure shift of a Raman line (c-BN, diamond). The calibration of those sensors are presented in detail, and discussion is made on their useful pressure and temperature ranges.     

A new type of compact large-capacity press for neutron and x-ray scattering

We present a new type of compact hydraulic press of 200?t capacity and 60?kg mass provided with two large openings of 140° (equatorial) x 60° (azimuthal) around the sample area. This device has been designed and optimized using finite element calculations, and was built and recently successfully tested. A smaller version with 50 tonnes capacity and 8?kg mass is also available. This ‘VX’ type Paris–Edinburgh press is expected to have numerous applications in neutron and X-ray scattering whenever large sample volumes (typically 1–100?mm³) are required, in particular for angle-dispersive powder neutron diffraction on reactor sources, single crystal neutron diffraction, and inelastic neutron and X-ray scattering.     

Experimental measurement of the electrical conductivity of pyroxenite at high temperature and high pressure under different oxygen fugacities

Electrical conductivities of pyroxenite were measured between frequencies of 10^?1 and 10⁶ Hz in a multi-anvil pressure apparatus using different solid buffers (Ni+NiO, Fe+Fe₃O₄, Fe+FeO and Mo+MoO₂) to stabilize the partial pressure of oxygen. The temperature ranged from 1073 to 1423 K (800 to 1200 °C) and the pressure from 1.0 to 4.0 GPa. We observe that: (1) the electrical conductivity (σ) of pyroxenite depends on frequency; (2) σ tends to increase with rising temperature (T), and Log σ and 1/T obey a linear Arrhenius relationship; (3) under control of the buffer Fe+Fe₃O₄, σ tends to decrease with rising pressure, nevertheless the activation enthalpy tends to increase. For the first time we have obtained values for the activation energy and activation bulk volume of the main charge carriers, which are (1.60±0.07) eV and (0.05±0.03) cm³/mol, respectively; (4) for a given pressure and temperature, σ tends to rise with increased oxygen fugacity, whereas the activation enthalpy and preexponential factor tend to decrease; and (5) the behaviour of the electrical conductivity at high temperature and high pressure can be reasonably interpreted by assuming that small polarons provide the dominant conduction mechanism in the pyroxenite samples.     

Study of partial melting at high-pressure using in situ X-ray diffraction

The high-pressure melting behavior of different iron alloys was investigated using the classical synchrotron-based in situ X-ray diffraction techniques. As they offer specific advantages and disadvantages, both energy-dispersive (EDX) and angle-dispersive (ADX) X-ray diffraction methods were performed at the BL04B1 beamline of SPring8 (Japan) and at the ID27-30 beamline of the ESRF (France), respectively. High-pressure vessels and pressure ranges investigated include the Paris–Edinburgh press from 2 to 17 GPa, the SPEED-1500 multi-anvil press from 10 to 27 GPa, and the laser-heated diamond anvil cell from 15 to 60 GPa. The onset of melting (at the solidus or eutectic temperature) can be easily detected using EDX because the grains start to rotate relative to the X-ray beam, which provokes rapid and drastic changes with time of the peak growth rate. Then, the degree of melting can be determined, using both EDX and ADX, from the intensity of diffuse X-ray scattering characteristic of the liquid phase. This diffuse contribution can be easily differentiated from the Compton diffusion of the pressure medium because they have different shapes in the diffraction patterns. Information about the composition and/or about the structure of the liquid phase can then be extracted from the shape of the diffuse X-ray scattering.     

Bulk moduli and high-pressure phases of the uranium rocksalt structure compounds: II. The monopnictides

Abstract

The high-pressure crystal structures of the compounds UX, where X = N, P, As and Sb, have been studied using X-ray diffraction in the pressure range up to about 60 GPa Rhornbohedral distortions are observed for UN and Up above 29 GPa and lO GPa, respectively. In Up a further transformation to an orthorhombic phase occurs at 28 GPa. UAs and USb transform to the CsCl structure at 20 GPa and 9 GPa, respectively. The latter transformations show a considerable hysteresis when the pressure is released. The scaling behaviour of the bulk modulus has been studied. It is confirmed that a log-log plot of bulk modulus versus specific volume for the cubic phases gives a straight line with a slope near ? 5/3.     

Semiconductor diamond heater in the Kawai multianvil apparatus: an innovation to generate the lower mantle geotherm

Semiconductor diamond is considered the best heater material to generate ultra-high temperatures in a Kawai cell. In two pioneering studies, a mixture of graphite and amorphous boron (or boron carbide, B₄C) was converted to semiconductor diamond in the diamond stability field and was confirmed to generate 2000°C and 3500°C, respectively. Following these works, we synthesized a homemade boron-doped graphite block with fine machinability. With this technical breakthrough, we developed a semiconductor diamond heater in a smaller Kawai-type cell assembly. Here, we report the procedure for making machinable boron-doped graphite, and the performance of the material as a heater in a Kawai cell at 15?GPa using tungsten carbide anvils and at ～50?GPa using sintered diamond anvils. Furthermore, we present a finite element simulation of the temperature distribution generated by a semiconductor diamond heater, which is much more homogeneous than that generated by a metal heater.