High-pressure phases of thorium and uranium compounds with the rocksalt structure

Abstract

The high-pressure crystal structures of the actinide compounds ThX and UX (X= C, N, P, S, As, Se, Sb, Te) have been studied by X-ray diffraction using synchrotron radiation, in the pressure range up to about 60 GPa Distorted fcc structures were observed for UC (27 GPa), UN (29 GPa), UP (10/28 GPa), US (10 GPa) and ThS (20 GPa). No phase transition has been observed for ThC and ThN. Compounds with As, Se, Sb all transform to the CsCl structure. ThP transform to the CsCl structure at 30 GPa. ThTe has the CsCl structure at ambient pressure and no further phase transition has been observed. UTe transforms to the CsCl structure at 9 GPa.     

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.     

Advances in data reduction of high-pressure x-ray powder diffraction data from two-dimensional detectors: a case study of schafarzikite (FeSb(2)O(4))

Methods have been developed to facilitate the data analysis of multiple two-dimensional powder diffraction images. These include, among others, automatic detection and calibration of Debye-Scherrer ellipses using pattern recognition techniques, and signal filtering employing established statistical procedures like fractile statistics.All algorithms are implemented in the freely available program package Powder3D developed for the evaluation and graphical presentation of large powder diffraction data sets.As a case study, we report the pressure dependence of the crystal structure of iron antimony oxide FeSb(2)O(4) (p≤21?GPa, T = 298?K) using high-resolution angle dispersive x-ray powder diffraction. FeSb(2)O(4) shows two phase transitions in the measured pressure range. The crystal structures of all modifications consist of frameworks of Fe(2+)O(6) octahedra and irregular Sb(3+)O(4) polyhedra. At ambient conditions, FeSb(2)O(4) crystallizes in space group P4(2)/mbc (phase I). Between p = 3.2?GPa and 4.1?GPa it exhibits a displacive second order phase transition to a structure of space group P 2(1)/c (phase II, a = 5.7792(4)??, b = 8.3134(9)??, c = 8.4545(11)??, β = 91.879(10)°, at p = 4.2?GPa). A second phase transition occurs between p = 6.4?GPa and 7.4?GPa to a structure of space group P4(2)/m (phase III, a = 7.8498(4)??, c = 5.7452(5)??, at p = 10.5?GPa). A nonlinear compression behaviour over the entire pressure range is observed, which can be described by three Vinet equations in the ranges from p = 0.52?GPa to p = 3.12?GPa, p = 4.2?GPa to p = 6.3?GPa and from p = 7.5?GPa to p = 19.8?GPa. The extrapolated bulk moduli of the high-pressure phases were determined to K(0) = 49(2)?GPa for phase I, K(0) = 27(3)?GPa for phase II and K(0) = 45(2)?GPa for phase III. The crystal structures of all phases are refined against x-ray powder data measured at several pressures between p = 0.52?GPa, and 10.5?GPa.     

Synthesis experiments on in-Sb and B-Sb systems in a laser heated diamond-anvil cell

Abstract

High pressure and high temperature synthesis experiments were carried out on In-Sb and B-Sb systems with a laser heated diamond-anvil cell. InSb was synthesized starting from In and Sb at various pressures ranging from 0.2 to 10 GPa. The cubic as well as the high pressure phases were successfully synthesized. Experiments above 8 GPa, wherein antimony exists in the tetragonal phase, have revealed no new phases of InSb. Trials of synthesizing a compound from B and Sb gave negative result to at least 30 GPa.     

Phase transitions of YbX (X = P,As and Sb) with a NaCl-type structure at high pressures

The powder X-ray diffraction of YbX (X?=?P, As and Sb) with a NaCl-type structure has been studied with synchrotron radiation up to 63?GPa at room temperature. YbSb undergoes the first-order structural phase transition from the NaCl-type (B1) to the CsCl-type (B2) structure at around 13?GPa. The structural change to the B2 structure occurs with the volume collapse of about 1% at 13?GPa. The transition pressure of YbSb is surprisingly lower than that of any other heavier LnSb (Ln?=?Dy, Ho, Er, Tm and Lu). The pressure-induced phase transitions in YbP and YbAs are observed at around 51?GPa and 52?GPa respectively. The transition pressure of both compounds is much higher than that of YbSb. The high-pressure structural behaviour of YbX (X?=?P, As and Sb) is discussed. The volume versus pressure curve for YbX with the NaCl-type structure is fitted by a Birch equation of state. The bulk moduli of these compounds with the NaCl-type structure are 104?GPa for YbP, 85?GPa for YbAs and 52?GPa for YbSb.     

Electronically induced lattice instabilities in b.c.c. Zr

Electronically induced lattice instabilities in metals are discussed by means of an accurate determination of the generalized susceptibility function, χ(q), from a KKR band structure and Fermi surface determined for b.c.c. Zr. We describe how the detailed behavior of χ(q) for b.c.c. Zr may be related to the omega phase upon alloying with Nb or upon application of pressure to the b.c.c. lattice.     

High-pressure Raman spectroscopy of antimony: As-type, incommensurate host-guest, and bcc phases

The vibrational dynamics of elemental solids that form incommensurate host-guest structures are of fundamental interest. High-pressure Raman scattering has been used to examine the vibrational spectrum of the group-V element Sb up to 33 GPa. A_1g and E_g phonons of the ambient pressure rhombohedral A7 phase display a marked decrease with pressure, i.e., prior to the transition to the tetragonal host-guest Sb-II phase at 8.6 GPa, via the monoclinic host-guest Sb-IV phase. The Raman spectrum of the incommensurate host-guest Sb-II phase, has five bands between 80 cm⁻¹ and 200 cm⁻¹ that increase with pressure. For the bcc structure stable above 28 GPa, we observe one weak disorder-induced band that increases with pressure.     

Relative stability of f.c.c. and b.c.c. structures for model systems at high temperatures

Summary Free-energy, entropy and volume differences between face-centered and body-centered cubic structures have been evaluated for model rare gas and alkali metal crystals by using the method of overlapping distributions. Stable phases are predicted in agreement with the behaviour of real materials in the regions of validity of classical mechanics and in agreement with the results of previous dynamical-simulation studies of crystal nucleation from the melt and of polymorphic transformations. The existence of a stable b.c.c. phase at high pressure and temperatures is predicted in this way for Lennard-Jones solids, while no high-pressure f.c.c. phase is expected for model Rb and Cs systems. We also show the possibility of making calculations of free-energy barriers to displacive crystalline transformations along a prescribed trajectory in configuration space. Work supported by the U.S. Department of Energy, Istituto per la Ricerca Scientifica e Tecnologica, Trento, and Gruppo Nazionale di Struttura della Materia del C.N.R., Italy.     

Synchrotron X-ray diffraction of SiO2 to multimegabar pressures

Abstract

α-Quartz was compressed at room temperature in a diamond-anvil cell without a medium to maximum pressures of 31 to 213 GPa and was studied by energy-dispersive synchrotron X-ray diffraction. Broad peaks observed in a previous high-pressure diffraction study of silica glass are evident in the present study of quartz compression, providing in situ confirmation of pressure-induced amorphization above 21 GPa. The 21-GPa crystalline-crystalline (quartz 1–11) transformation previously observed on quasihydrostatic compression of quartz is found to also occur under the current nonhydrostatic conditions, at the identical pressure. With nonhydrostatic compression, however, new sharp diffraction lines are observed at this pressure. The measurements show the coexistence of at least one amorphous and two crystalline phases above 21 GPa and below 43 GPa. The two crystalline phases are identified as quartz II and a new, high-pressure silica phase. The high-pressure phases, both crystalline and amorphous, can be quenched to ambient conditions from a maximum pressure of 43 GPa. With compression above 43 GPa, the diffraction pattern from quartz II is lost and the second crystalline phase persists to above 200 GPa.     

Magnetic neutron diffraction under pressures up to 43 GPa. Study of the EuX and GdX compounds

We present some recent results on magnetic neutron studies at pressures above 40 GPa. We used diamond and sapphire anvil pressure cells for low temperature neutron studies and a powder diffractometer specialized for high pressure studies. Focusing systems and low-background conditions allowed us to study samples with volumes as small as 0.001 mm³ in a diamond anvil cell at a pressure of 50 GPa. This technical progress allowed us to obtain new results in studies of “textbook” magnetic insulators EuX (X = S, Se, Te) and GdX (X = As, Sb, Bi). We found new magnetic phases. In the Eu-chalcogenides we observed a strong anion-dependent increase of the ferromagnetic exchange with decreasing lattice constant. In contrast, in the GdX compounds the antiferromagnetic order remains stable up to a pressure of 43 GPa. We show the importance of our results to understand the origin of indirect exchange interactions in magnetic semiconductors with well localized magnetic shells. This revised version was published online in July 2006 with corrections to the Cover Date.     

硫酸锂钾的高压相及室温以上的P-T状态图

本文用改进了的高压下差热分析方法以及金刚石压砧加温下的X射线衍射方法研究了硫酸锂钾(LiKSO₄)在室温以上的高压相变,较精确地测定了在3GPa、800℃以下各相的平衡条件,作出了它的P-T状态图。本文发现LiKSO₄在1.65GPa以上压力存在一个高压结构,标定了它的晶体参数,测量了它在高压下的热膨胀行为,并研究了高压相在常压时的热稳定性。 关键词：     

Pressure-induced phase transition(s) in KMnF3 and the importance of the excess volume for phase transitions in perovskite structures

We report a pressure-dependent investigation of KMnF(3) by x-ray diffraction up to 30 GPa. The results are discussed in the framework of Landau theory and in relation to the isostructural phase transition in SrTiO(3). The phase transition temperature near 186 K in KMnF(3) shifts to room temperature at a critical pressure of P(c) = 3.4 GPa; the pressure dependence of the transition point follows ΔP(c)/ΔT(c) = 0.0315 GPa K(-1). The transition becomes second order under high pressure, close to the tricritical point. The phase transition is determined by the rotation of MnF(6) octahedra with their simultaneous expansion along the rotation axis. The rotation angle was found to increase to 10.5° at 24 GPa. An additional anomaly was observed at higher pressure around 25 GPa, suggesting a further phase transition.     

The baddeleyite-type high pressure phase of Ca(OH)2

Abstract

A phase transition from Ca(OH)₂ I (portlandite) to Ca(OH)₂ II at high pressure and temperature has been confirmed, using in situ x-ray diffraction in a multianvil high pressure device (DIA). The structure was determined at 9.5 GPa and room temperature from data collected after heating the sample at 300°C at 7.2 GPa in a diamond anvil cell. Both the Le Bail fit and preliminary Rietveld refinement suggest that the new phase, which reverts to Ca(OH), I during pressure release, has a structure related to that of baddeleyite (ZrO₁); it is monoclinic (P2₁/c) with a= 4.887(2), b= 5.834(2), c = 5.587(2), β = 99.74(2)°. The coordination number of Ca increases from six to seven (5 + 2) across the transition. At 500°C, the phase boundary is bracketed at 5.7 ± 0.4 GPa by reversal experiments performed in the DIA.     

Superconducting phase diagram of Li metal in nearly hydrostatic pressures up to 67 GPa

The dependence of the superconducting transition temperature T(c) on nearly hydrostatic pressure has been determined to 67 GPa in an ac susceptibility measurement for a Li sample embedded in helium pressure medium. With increasing pressure, superconductivity appears at 5.47 K for 20.3 GPa, T(c) rising rapidly to approximately 14 K at 30 GPa. The T(c)(P) dependence to 67 GPa differs significantly from that observed in previous studies where no pressure medium was used. Evidence is given that superconductivity in Li competes with symmetry breaking structural phase transitions which occur near 20, 30, and 62 GPa. In the pressure range 20-30 GPa, T(c) is found to decrease rapidly in a dc magnetic field, the first evidence that Li is a type I superconductor.     

LiAl5O8高压相变研究

 运用金刚石压砧同步辐射X射线衍射,对尖晶石结构的LiAl₅O₈进行了高压原位研究。实验发现：在高压下,一组LiAl₅O₈的新相衍射峰出现,随着压力的增加,其新相衍射峰逐渐增强,当压力增加到45.0 GPa时,LiAl₅O₈的低压相衍射峰全部消失,而形成了一组高压新相衍射峰。采用指标化程序对衍射数据进行处理和分析,确定这一高压新相为正交晶系结构,其晶胞参数为a=0.995 9 nm,b=0.644 7 nm,c=0.333 4 nm ,空间群为Pmm2。     

Pressue Dependence of the Ferroelectric-Paraelectric Transition Temperature in KNBO 3 . Comparision with the Ice VII-VIII Transition

New results on the phase diagram of KNbO 3 determined, from 10 to 650 K up to 30 GPa, with Raman scattering are given. On increasing pressure the Curie temperature T c was found to shift down regularly from 700 K, at atmospheric pressure, to 20 K at ～25 GPa. Up to 20 GPa, the pressure dependence of T c follows a classical regime described by the Ising model where the dipolar interaction follow a i 2 /v law, where i is the off-center displacement and v the unit cell volume. This behaviour found also for the ice VII-VIII is very likely encountered in a number of (anti)ferroelectric-paraelectric transformations involving positional disorder.     

First principles study of isostructural phase transition in Sb2Te3 under high pressure

The structural properties, electronic band structure and Bader charge of Sb₂Te₃ under hydrostatic pressure were simulated using density functional theory in order to study isostructural phase transitions (IPT) in Sb₂Te₃. The theoretical results showed that the axial ratio c /a did not exhibit any anomaly below 6 GPa. The variations of bond lengths were discontinuous at 2.5 GPa, which suggested considerable changes in interatomic interactions and provided sound support to the IPT. The effective charges of Sb and Te atoms showed significant discontinuous variations at 2.5 GPa, which revealed a strong redistribution of the electronic charge density and considerably changed interactions among bonding atoms. Thus, the IPT is originated from the considerable variation in the electronic charge density. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

β-FeSi2的高压研究

 对β-FeSi₂晶体进行了原位X射线衍射高压研究。利用同步辐射X射线衍射原位研究了β-FeSi₂的高压相演化，发现压力在4.3 GPa时出现相变，在25.8 GPa时相变完成。指标化结果表明：经高压处理后得到的产物具有四方结构，其晶格常数为：a=b=1.004 9 nm，c=0.339 4 nm。     

High-pressure Raman study of solid hydrogen up to 300 GPa

The high-pressure behavior of solid hydrogen has been investigated by in situ Raman spectroscopy upon compression to 300 GPa at ambient temperature. The hydrogen vibron frequency begins to decrease after it initially increases with pressure up to 38 GPa. This softening behavior suggests the weakening of the intramolecular bond and the increased intermolecular interactions. Above 237 GPa, the vibron frequency softens very rapidly with pressure at a much higher rate than that of phase III, corresponding to transformation from phase III into phase IV. The phase transition sequence has been confirmed from phase I to phase III and then to phase IV at 208 and 237 GPa, respectively. Previous theoretical calculations lead to the proposal of an energetically favorable monoclinic C2/c structure for phase III and orthorhombic Pbcn structure for phase IV. Up to 304 GPa, solid hydrogen is not yet an alkali metal since the sample is still transparent.     

Crystal structure of the high pressure phases of bismuth bi iii and bi iii′ by high energy synchrotron x-ray diffraction

Abstract

This paper reports the results of a synchrotron X-ray diffraction study on the crystal structures of Bi 111 and Bi 111′ which have been known to form under high pressure but have, for a long time, been unsolved. Powdered samples were compressed in a cubic-type multi-anvil press, MAXID, and diffraction data were collected using an Imaging Plate with monochromatized radiation of an energy of 49.7 keV. It was possible to identify at 3.8 GPa forty-eight reflections for Bi I11 in the sin θ / δ range from 1.6 nm^?1 to 5.6 nm^?1, which were indexed in terms of a tetragonal unit cell with a=0.8659 nm and c═ O·4238 nm (2=10). Analysis based on the observed intensities of the reflections led to a structure in which atoms form a distorted body-centered cubic lattice. It is of the same type as the structure of the high pressure phase of antimony Sb 11. When pressure was increased across the suggested transition pressure 4.3 GPa between Bi III and Bi III′ to 6.6 GPa, no change in the diffraction pattern was observed, indicating that there is no distinction between the two phases as long as the crystal structure is concerned. Discussion is given on the sequence of high pressure phase transitions in the Group Vb elements.