High Pressure X-Ray Absorption and Diffraction Study of InAs

We have performed X-ray absorption (XAS) and diffraction (XRD) measurements at high pressure on samples of powdered InAs, up to 50 and 80 GPa, respectively. In the lower pressure range, our data are consistent with the following structural sequence: Zincblende M NaCl M Cmcm . The first order transition from the semiconducting Zincblende phase to the metallic NaCl phase is clearly seen by the shift in the absorption onset at the As K-edge and the strong modifications of the extended X-ray absorption fine structure (EXAFS) due to the changes in the local structure from a 4-fold to a 6-fold coordinated environment. XAS shows the high pressure phase to be locally site-ordered. The diffraction data, analized by Rietveld fitting, gives a volume discontinuity of j V/V 0 ～0.18 for the first order transition. There is no apparent volume discontinuity associated to the NaCl M Cmcm transition.     

Suppression of Jahn-Teller Distortion and Insulator-To-Metal Transition in LaMnO 3 at High Pressures

Structural, vibrational and electronic properties of LaMnO 3 under pressures up to 38 GPa have been studied by synchrotron X-ray powder diffraction, Raman spectroscopy, optical reflectivity, and transport measurements. The cooperative Jahn-Teller distortion of the MnO 6 octahedra of the perovskite-type structure is continuously suppressed with increasing pressure, a process which appears completed at ～20 GPa. The system remains insulating to 32 GPa, where an insulator-metal transition is observed. This transition is attributed to strengthened Mn--O--Mn interactions due to the increasing overlap of atomic orbitals.     

High pressure X-ray diffraction experiments on NpS and PUS up to 60 GPa

Abstract

Neptunium and plutonium monosulfides were studied under high pressure up to ～60 GPa using a diamond anvil cell in an energy dispersive X-ray diffraction facility. The compounds, of cubic rock salt structure type at ambient pressure, do not show any crystallographic phase transition in the domain of investigation. From the pressure-volume relationship, we determined bulk moduli of 92 and 120 GPa with pressure derivatives of 4.6 and 4.1 for NpS and PUS respectively.     

Crystal Structure Transformations of Rare-Gas Solids Under Pressure

Pressure-induced structural changes in solid krypton (Kr) and xenon (Xe) have been studied using angle dispersive X-ray diffraction in a diamond-anvil cell (DAC) up to 50 GPa. The analysis of the results shows that in solid Kr (Xe) the phase transition from fcc to hcp starts below 3.2 GPa (1.5 GPa). Albeit the hcp/fcc ratio increases under pressure, both phases coexist up to the highest pressure reached in this study. Room temperature (RT) equations of state (EOS) are determined.     

B-C-N Compound Synthesized Under High Temperature and High Pressure

Crystalline hexagonal B(N 1 m x C x ) and cubic B-C-N compounds have been synthesized from a precursor produced from melamine and boric acid by application of high temperature and high pressure. The synthesized products were characterized by X-ray diffraction. The lattice parameters for the hexagonal crystal are a=2.506 Å, c=6.657 Å, and that for the cubic crystal is a=3.596 Å. The X-ray photoelectron spectra of the B-C-N compound indicate the presence of B-N, C-N, C-C, and B-C bonds, which suggests that boron, carbon, and nitrogen atoms all bond with one another and that the B-C-N crystal is a compound in which the three kinds of atoms are mixed atomically. The composition of the B-C-N compound is B 0.47 C 0.23 N 0.30 . A strong absorption band at 1000～1120 cm m 1 attributable to the cubic B-C-N phase is observed in the infrared spectrum. The photoluminescence spectrum of hexagonal B-C-N powder measured at room temperature features a broad peak centered at 374 nm, corresponding to the band-edge emission of h-B-C-N, and is similar to that of w-GaN.     

X-Ray Diffraction Investigation of Oleic Acid under High Pressure

Pressure has a specific influence on the light scattering in those liquids in which all molecules have an unsaturated double bond C=C. Strong changes of intensity of transmitted and scattered light in oleic acid were observed during its transition to the high-pressure phase. In this paper, local order in liquid of oleic acid has been studied using the X-ray diffraction photographic Laue method. Experiments were run at room temperature under atmospheric pressure as well as under pressures up to 0.25 GPa. At pressures above 0.2 GPa a strong increase of ordering of molecules, similar to a smectic liquid crystal phase, has been observed. This confirms results obtained previously by studies of light scattering under high pressure.     

高压下β-FeOOH纳米固体结构转变的研究

 以化学水解法合成的β-FeOOH纳米微粉（平均粒径在12 nm左右）为原料，分别在0.0~4.5 GPa和200~350 ℃的压力和温度范围进行冷压和热压处理。实验结果表明，冷压对β-FeOOH纳米固体的结构没有明显影响，但却使它的热致相变（从β-FeOOH相到α-Fe₂O₃相）温度从常压下的203.8 ℃提高到4.5 GPa压力下的274 ℃，接近常规体相材料的相变温度。而在一定的热压条件处理下，首次发现了从β-FeOOH相到α-FeOOH相的结构转变，并在4.5 GPa、200 ℃的热压条件下得到了转变过程中的一个新的亚稳相。从压力和温度对纳米微粒的作用角度，对上述实验结果进行了讨论。     

Optimization of Paris–Edinburgh press cell assemblies for in situ monochromatic X-ray diffraction and X-ray absorption

We describe some important improvements allowed by the development of new cell assemblies coupled to opposed conical sintered diamond anvils in the Paris–Edinburgh press. We provide X-ray absorption and diffraction experiments carried out at pressures up to 16.5 GPa. The maximum temperature reached was 1800 K for P<10 GPa and 1300 K for higher pressures. The sintered diamond anvils are X-ray transparent and give access to a much larger X-ray window than the tungsten carbide anvils, even at the highest pressure. Therefore, X-ray measurements are performed using in situ cross-calibration simultaneously. We also describe a new heating setup used to reach high temperatures, despite the low conductivity of the sintered diamond core by deviating the electrical current using copper strips. These improvements are illustrated by recent data collected using angle dispersive in situ X-ray diffraction on liquid Fe-18%wt S and using EXAFS at the barium K-edge on Ba₈Si₄₆ silicon clathrates and at the iodine K-edge on iodine-intercalated nanotubes.     

Combined X-ray absorption and X-ray diffraction under high pressure

ABSTRACT

X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) are two complementary structural techniques. Their combination improves the understanding of the effect of pressure on materials as illustrated by examples taken from studies on different types of materials (semiconductors, molecular solid, ferroelectric perovskite and gas mixture). The introduction of nanopolycrystalline diamonds anvils has extended XAS to high-energy edges with the possibility to use energy-scanning XAS beamlines where XRD can be performed in addition to XAS experiments.     

一套高温高压原位拉曼散射、布里渊散射测量系统

本文描述了一套利用激光加热技术、金刚石对顶砧高压技术,集成共聚焦拉曼光谱测量、六通道布里渊散射光谱测量、以及黑体辐射光谱测温,成功搭建起来的高温高压原位拉曼散射、布里渊散射的光学测量系统。利用该系统,并结合薄膜沉积金属、光刻技术改进了金刚石对顶砧中样品的装填方法,解决了样品透明不易加热的问题。已利用该系统得到液态氩在0.85 GPa常温状态下和14.58 GPa熔融状态下的体声速分别为1.85 Km/s和5.19 Km/s。     

High pressure neutron diffraction studies using the Paris-Edinburgh cell

Abstract

Neutron diffraction was until recently confined to pressures below ～ 3 GPa. This restricted range has limited the high-pressure structural information that is available for a wide range of phenomena for which neutron diffraction is the technique of choice. But now the recently-developed Paris-Edinburgh cell can achieve pressures up to ～ 30 GPa with a sample volume large enough to allow accurate structural studies with neutrons. After a period of development of the neutron scattering techniques needed to obtain the best possible results using the cell, a variety of successful structural studies have been performed. These illustrate the value of neutron diffraction in important areas such as locating hydrogen and other low-Z atoms in structures, the measurement of accurate structural pressure dependence and the examination of the changes in atomic thermal motion with pressure.     

Density measurements of non-crystalline materials under high pressure and high temperature

Abstract

We have developed a new method for density measurements by means of X-ray absorption under high pressure and high temperature using a multi-anvil apparatus combined with a synchrotron-radiation source. To overcome the effect of the variation of the sample thickness under pressure, a sapphire ball was put in the sample capsule as a calibrant of the thickness, and the intensity of the transmitted X-ray beam was measured as a function of the sample position. The densities of crystalline and liquid tellurium were measured up to 5 GPa and up to 700°C. Discontinuous changes in the density at the Te I-Te 11 transition and at the melting were clearly observed.     

High pressure X-ray diffraction studies on UAI2, UAI2, and UAI4 systems

Abstract

The UAI₂, UAI₂, AND UAI₄ compounds have been studied by high pressure X-ray diffraction up to a maximum pressure of ～ 35 GPa. The compressibility behaviour of UAI₂ has been found to be consistent with the itinerant 5f states, whereas that of UAI₂ and UAI₄, indicate a more localized nature. Further, UAI₂ has been found to undergo a structural transition at ～ 11 GPa and the structure of the high pressure phase has been identified to be of MgNi₂ type with space group P6₃/mmc. The structure of UAI₂ at ambient pressure is of MgCu₂ type with space group Fd3m. From the electronic considerations, for instance, free electrons per atom ratio e/a, it is anticipated that it may transform back to MgCu₂ type structure at still higher pressures. On similar considerations, it is expected that most of the AB₂ type Laves phase compounds of the ‘f’ electron systems may undergo the structural sequence: MgCu₂ – MgZn₂ (or MgNi₂) – MgCu₂ due to increased delocalization of their ‘f’ electron states.     

High hydrostatic pressure ESR manostats

Abstract

Two high pressure X-band ESR resonators for sensitive measurements are described. Both systems have 100 kHz internal modulation coils and can cooperate with any standard ESR spectrometer. These cavities operate in two different temperature and pressure ranges: 77–400 K, up to 0.8 GPa and liquid helium temperature range, up to 1 GPa, respectively. Additionally, the cavity operating in the 77–400 K temperature range enables Photo-ESR measurements to be carried out.     

Phase transition in Pd_(40)Ni_(10)Cu_(30)P_(20) bulk metallic glass under HP & HT

Bulk metallic glass (BMG) can be regarded as a metallic solid with a frozen-in melt structure which lacks atomic periodicity. Generally, BMG is not in an internal equilib- rium state (IES) but may change to the IES when it obtains an appropriate energy to overcome the energy barrier. High pressure and temperature can be a driving force to cause various transitions in amorphous materials, such as a transition from the amor- phous to the crystalline[1―8] or from the crystalline to the amorp…     

Opposed type double stage cell for Mbar pressure experiment with large sample volume

ABSTRACT

A new opposed type double-stage large volume cell has been developed to compress large volume samples to more than 100?GPa (Mbar) pressure. A pair of second-stage diamond anvils is introduced into the first-stage Paris–Edinburgh press. The double-stage large volume cell allows the generation of ultrahigh pressures using a large culet diameter of the second-stage diamond anvils (diameters of 0.5–1.2?mm). Pressure generation up to 131?GPa has been achieved by using the culet diameter of 0.5?mm. Sample volume of the double-stage large volume cell can be more than ～100 times larger than that of conventional Mbar experiment using a diamond anvil cell. The double-stage large volume cell has a large opening in the horizontal plane for X-ray measurements, which is particularly suited for the multi-angle energy dispersive X-ray diffraction measurement, thus opening a new way of in situ structural determinations of amorphous materials at Mbar pressures.     

Pressure-Effect on Anatase Titanium Dioxide

Pressure-induced phase transition of anatase titanium dioxide was investigated by Raman, absorption spectroscopy and X-ray diffraction. The change in Raman and absorption spectra with pressure revealed that the transition from anatase to high pressure phase with f -PbO 2 structure (TiO 2 -II) occurred in the pressure range of 4.0-4.6 GPa for a single crystal. The X-ray powder diffraction patterns indicate the presence of superstructural lattice of anatase at pressures more than 3 GPa. The superstructure of anatase disappears on the release of the pressure. A sluggish transition to the high pressure phase is also observed. The anatase coexists with the high pressure phase at 5.2 GPa. The difference in the results between optical spectroscopy (single crystal) and X-ray diffraction (powder) will be due to crystalinity of the sample.     

Phase transition in Pd40Ni10Cu30P20 bulk metallic glass under HP & HT

The phase transitions in Pd40Ni10Cu30P20 bulk metallic glass (BMG) have been studied under high pressure and high temperature (HP & HT) by X-ray diffraction measurements with synchrotron radiation source. We found that the BMG underwent a phase transitions of amorphous-crystalline-amorphous at 10 GPa upon heating. The parallel experiments were carried out at 7 GPa, while we did not observe the amorphous-crystalline-amorphous transitions by increasing temperature. Quenching the melted BMG at 7 GPa, it was found that the phase crystallized from the melt differed from the primary phase crystallized from the starting amorphous solid upon heating, suggesting there existed a distinct mechanism in two cases.     

Applications of nano-polycrystalline diamond anvils to X-ray absorption spectroscopy under high pressure

ABSTRACT

Recently, nano-polycrystalline diamond (NPD) anvils have been widely applied in high pressure research using X-ray absorption spectroscopy (XAS). The nanometer-sized polycrystallization in NPD anvils enables us to obtain glitch-free X-ray absorption spectra. This advantage of NPD anvils drastically improves the experimental conditions of XAS, which has previously used conventional single-crystal diamond (SCD) anvils. Distorted spectra due to the glitches from the SCD anvils have been an inevitable problem of XAS. This paper reviews recent studies of XAS and related spectroscopic techniques using the NPD anvils, which have mainly been performed on BL39XU of SPring-8. We demonstrate how NPD anvils are useful when using XAS for high pressure research.     

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.