In situ mapping of high-pressure fluids using hydrothermal diamond anvil cells

We present new results combining high pressures and temperatures attainable in a diamond anvil cell with in situ synchrotron radiation induced micro-X-ray fluorescence measurements. Hydrothermal diamond anvil cells experiments have been performed by measuring the partitioning of Pb between aqueous fluids (pure water or NaCl-enriched water) and hydrous silicate melts of haplogranite composition using synchrotron X-ray fluorescence. The in situ measurements were performed in the range 0.3–1.2 GPa and 730–850 ^°C both in the aqueous fluid and in the silicate melts being in equilibrium. Pb is strongly partitioned into high-pressure–temperature hydrous melts when Cl is present in either the hydrous melt or the aqueous fluid. Moreover, our comparisons of in situ results with post-mortem results show that significant changes take place during rapid quenching especially when samples are small (few hundred of microns in diameter). Water exsolution is induced by the quench in the silicate melt showing the high mobility of Pb which immediately partitions into the water vapor phase during the quench. The current in situ approach offers thus a pertinent complementary method to the classical experimental petrology investigations.     

High pressure generation using double-stage diamond anvil technique: problems and equations of state of rhenium

We have developed a double stage diamond anvil cell (ds-DAC) technique for reproducible pressure by precisely fabricating 2nd stage anvils using a focused ion beam system. We used 2nd stage micro-anvils made of ultra-fine (V/V₀?=?0.633 for the smallest d-spacing. The calculated pressure for this minimum volume varies from 430 to 630?GPa, depending on the choice of the equation of state of rhenium. We conclude that the most likely pressure achieved for the minimum volume of rhenium is in a range of 430–460?GPa based on a calibration using the platinum pressure scale to 280?GPa and the latter value of 630?GPa is unreasonably high, suggesting that the pressures in an earlier study for the equation of state of rhenium would have been significantly overestimated.     

Equation of state of boron subarsenide B12As2 to 47 GPa

Compressibility of boron subarsenide B₁₂As₂ has been studied by synchrotron X-ray diffraction up to 47?GPa at room temperature in a diamond anvil cell using Ne pressure transmitting medium. A fit of experimental p–V data by Vinet equation of state yielded the bulk modulus of 150(4) GPa and its first pressure derivative of 6.4(3). No pressure-induced phase transitions have been observed.     

Single-crystal X-ray diffraction at megabar pressures and temperatures of thousands of degrees

The most reliable information about crystal structures and their response to changes in pressure and temperature is obtained from single-crystal diffraction experiments. We have developed a methodology to perform single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells and demonstrate that structural refinements and accurate measurements of the thermal equation of state of metals, oxides and silicates from single-crystal intensity data are possible in pressures ranging up to megabars and temperatures of thousands of degrees. A new methodology was applied to solve the in situ high pressure, high temperature structure of iron oxide and study structural variations of iron and aluminum bearing silicate perovskite at conditions of the Earth's lower mantle.     

金刚石压砧内单轴应力场对物质状态方程测量的影响

金刚石压砧的几何结构使得在高压下封垫内的样品通常处于单轴应力场中：压砧轴向加载应力最大,径向应力最小.由于金刚石压砧内非静水压单轴应力场的影响,用传统的高压原位X射线衍射方法测得的物质压缩曲线一般位于理想静水压压缩曲线之上.利用金刚石压砧径向X射线衍射技术以及晶格应变理论,结合最近的钨、金刚石和硼六氧样品的高压原位同步辐射径向X射线衍射实验结果,从宏观差应力、样品强度、标压物质和待测物质强度的关系三个方面分析讨论了金刚石压砧内单轴应力场对物质状态方程测量的影响及解决方案. 关键词： 金刚石压砧 单轴应力场 高压原位X射线衍射 状态方程     

Determination of the phase boundary of GaP using in situ high pressure and high-temperature X-ray diffraction

The high pressure behavior of gallium phosphide, GaP, has been examined using the synchrotron X-ray diffraction technique in a diamond anvil cell up to 27?GPa and 900?K. The transition from a semiconducting to a metallic phase was observed. This transition occurred at 22.2?GPa and room temperature, and a negative dependence of temperature of this transition was found. The transition boundary was determined to be P (GPa)?=?22.6???0.0014?×?T (K).     

A combination of a Drickamer anvil apparatus and monochromatic X‐rays for stress and strain measurements under high pressure

A modified Drickamer anvil apparatus has been developed to combine with monochromatic synchrotron radiation for high‐pressure X‐ray diffraction and radiography in the GSECARS bending‐magnet station, 13‐BM‐D, at the Advanced Photon Source, Argonne, USA. Using this experimental set‐up, deformation experiments can be carried out at pressures in excess of 30 GPa at high temperatures. Differential stresses and total axial strains of polycrystalline platinum and Mg₂SiO₄ ringwoodite have been measured up to 32 GPa at room temperature using tungsten carbide anvils. The total axial strain of the platinum increases with pressure and reaches about 55% at the highest pressure. A test run using a composite sintered diamond anvil system was performed. The use of X‐ray‐tranparent anvils enables the entire Debye rings to be observed up to 10° 2θ. With high‐energy photons (65–70 keV), this allows a coverage in Q (= 2π sinθ/λ) to about 3 Å^?1, thus making it possible to evaluate hydrostatic pressure and differential stress in crystalline minerals using diffraction. This, coupled with the ability to determine axial strain, allows deformation studies to be performed to pressures above 30 GPa.     

Strength and equation of state of molybdenum triboride under 80 GPa pressure,using radial X-ray diffraction

The strength and equation of state of molybdenum triboride have been determined under nonhydrostatic compression up to 80?GPa, using an angle-dispersive radial X-ray diffraction technique in a diamond anvil cell (DAC). The RXD data yield a bulk modulus and its pressure derivative as K_0?=?342(6)?GPa with K₀′?=?2.11(17) at ψ?=?54.7°. Analysis of diffraction data using the strain theory indicates that the ratio of differential stress to shear modulus (t/G) ranges from 0.002 to 0.050 at pressures of 4–80?GPa. Together with theoretical results on the high pressure shear modulus, our results here show that molybdenum triboride sample under uniaxial compression can support a differential stress of ～10?GPa when it started to yield with plastic deformation at ～30?GPa. In addition, we draw a conclusion that MoB₃ is not a superhard material but a hard material.     

Diamond anvils with a spherical support designed for X-ray and neutron diffraction experiments in DAC

Here, we present new diamond anvils with a spherical support designed for applications in diamond anvil cell (DAC) technique. The main feature of the anvils is the diamond crown of a spherical shape. The assembly of the spherical diamond fixed within a spherical support of a seat made of tungsten carbide or hard metals provides enhanced stability, simple alignment, and large optical and X-ray aperture that makes it very useful for broad applications in DAC technique, particularly for single crystal X-ray and powder neutron diffraction. The anvils were tested in various experiments conducted in a wide pressure–temperature range and showed a very good performance.     

Melting of B12P2 boron subphosphide under pressure

Melting of boron subphosphide (B₁₂P₂) to 26?GPa has been studied by in situ synchrotron X-ray powder diffraction in a laser-heated diamond anvil cell, and by quenching and electrical resistance measurements in a toroid-type high pressure apparatus. B₁₂P₂ melts congruently, and the melting curve has a positive slope of 23(6)?K/GPa. No solid-state phase transition was observed up to the melting in the whole pressure range under study.     

A system for doing low temperature-high pressure single crystal X-ray diffraction with a synchrotron source

Abstract

A new diamond anvil cell and a helium flow cryostat have been developed for X-ray diffraction on single crystals at low temperatures and high pressures using white radiation of a synchrotron beam. This novel instrument especially enables continuous change of temperature and pressure of the sample without any adjustment of alignment. Automatic search for diffraction peaks can be performed since less than 30 pm eccentricity can be maintained during the rotation of the cell in the cryostat and the rotation of the cryostat on the goniometer head. The minimum temperature reached is 46 K. Measurements of solid 4He at 11.8 GPa are presented which confirm the stability of the hcp phase on this isobar.     

High pressure studies using two-stage diamond micro-anvils grown by chemical vapor deposition

Ultra-high static pressures have been achieved in the laboratory using a two-stage micro-ball nanodiamond anvils as well as a two-stage micro-paired diamond anvils machined using a focused ion-beam system. The two-stage diamond anvils’ designs implemented thus far suffer from a limitation of one diamond anvil sliding past another anvil at extreme conditions. We describe a new method of fabricating two-stage diamond micro-anvils using a tungsten mask on a standard diamond anvil followed by microwave plasma chemical vapor deposition (CVD) homoepitaxial diamond growth. A prototype two-stage diamond anvil with 300?µm culet and with a CVD diamond second stage of 50?µm in diameter was fabricated. We have carried out preliminary high pressure X-ray diffraction studies on a sample of rare-earth metal lutetium sample with a copper pressure standard to 86?GPa. The micro-anvil grown by CVD remained intact during indentation of gasket as well as on decompression from the highest pressure of 86?GPa.     

High pressure X-ray diffraction and Raman spectroscopic studies of the phase change of D2O ice VII at approximately 11 GPa

High pressure experiments were performed on D₂O ice VII using a diamond anvil cell in a pressure range of 2.0–60 GPa at room temperature. In situ X-ray diffractometry revealed that the structure changed from cubic to a low symmetry phase at approximately 11 GPa, based on the observed splitting of the cubic structure's diffraction lines. Heating treatments were added for the samples to reduce the effect of non-hydrostatic stress. After heating, splitting diffraction lines became sharp and the splitting was clearly retained. Although symmetry and structure of the transformed phase have not been determined, change in volumes vs. pressure was calculated, assuming that the low-symmetry phase had a tetragonal structure. The bulk modulus calculated for the low-symmetry phase was slightly larger than that for the cubic structure. In Raman spectroscopy, the squared vibrational frequencies of ν₁ (A_1g), as a function of pressure, showed a clear change in the slope at 11–13 GPa. The full width at half maxima of the O-D modes decreased with increasing pressure, reaching a minimum at approximately 11 GPa, and increased again above 11 GPa. These results evidently support the existence of phase change at approximately 11 GPa for D₂O ice VII.     

High pressure behavior of nano-crystalline CeO2 up to 35 GPa: a Raman investigation

The present paper reports the results of in situ Raman studies carried out on nano-crystalline CeO₂ up to a pressure of 35 GPa at room temperature. The material was characterized at ambient conditions using X-ray diffraction and Raman spectroscopy and was found to have a cubic structure. We observed the Raman peak at ambient at 465 cm^?1, which is characteristic of the cubic structure of the material. The sample was pressurized using a diamond anvil cell using ruby fluorescence as the pressure monitor, and the phase evolution was tracked by Raman spectroscopy. With an increase in the applied pressure, the cubic band was seen to steadily shift to higher wavenumbers. However, we observed the appearance of a number of new peaks around a pressure of about 34.7 GPa. CeO₂ was found to undergo a phase transition to an orthorhombic α -PbCl₂-type structure at this pressure. With the release of the applied pressure, the observed peaks steadily shift to lower wavenumbers. On decompression, the high pressure phase existed down to a total release of pressure.     

On-line laser heating setup for ED-XAS at ID24: preliminary optical design and test results

Double-sided laser heating (LH) combined with synchrotron X-ray radiation for in situ studies in the diamond anvil cell (DAC) has been the most productive and widely used high-temperature–high pressure technique in the past two decades. In the framework of the UPBL11 project (upgrade of ID24 beamline of European Synchrotron Radiation Facility), we developed a new on-line LH system for DACs. The preliminary optical scheme of the system is presented and discussed. Varying the settings, we are able to shape and to size the beam on the surface of the sample in the DAC. First pilot applications to the Fe case are shown.     

Methodology for in situ synchrotron X-ray studies in the laser-heated diamond anvil cell

ABSTRACT

A review of some important technical challenges related to in situ diamond anvil cell laser heating experimentation at synchrotron X-ray sources is presented. The problem of potential chemical reactions between the sample and the pressure medium or the carbon from the diamond anvils is illustrated in the case of elemental tantalum. Preliminary results of a comparison between reflective and refractive optics for high temperature measurements in the laser-heated diamond anvil cell are briefly discussed. Finally, the importance of the size and relative alignment of X-ray and laser beams for quantitative X-ray measurements is presented.     

外加热型金刚石对顶压砧高压装置及高温下的压力测量

 本文报导了一种外加热型金刚石对顶压砧装置的高温高压技术，装置的压力可达20 GPa，温度可达350 ℃。采用本装置对六角结构的α-LiIO₃进行了高温高压X射线衍射实验，获得的四方结构高压相与用淬火卸压所得的ε相结构一致；建立了高温下的红宝石测试技术。发现可以根据由此法测定的Δγ_p-T曲线初步判别样品是否存在伴随有体积变化的结构相变，并可估计出该相变的压力、温度范围及相变造成的压力下降值。     

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.     

Single crystal x-ray diffraction with a synchrotron source in a mdac at low temperature

Abstract

A new diamond anvil cell and a helium flow cryostat have been developed for x-ray diffraction on single crystals at low temperatures and high pressures using the white radiation of a synchrotron beam. This novel instrument especially enables continuous change of sample temperature and pressure without any adjustment of alignment. A minimum temperature of 46 K has been reached.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

Studies on Im-3-type KSbO3 using high pressure X-ray diffraction and Raman spectroscopy

In situ X-ray diffraction and Raman scattering experiments using a diamond anvil cell revealed that Im-3-type KSbO₃ remains stable up to 40.5?GPa with a bulk modulus K₀?=?101.6 (7)?GPa. Rietveld structure refinements and mode Grüneisen parameters suggested that the stability mechanism of this three-dimensional cubic tunnel structure was attributed to the isotropic compression for all types of Sb–O bonding in the unit of SbO₆ octahedron. Isotropic structure adjustment with external pressure reflected the nature that Im-3-type KSbO₃ model structure has a high ionic tolerance with a change in the chemical pressure in the isomorphous substitutions.