High-pressure structural phase stability in Hg TO 1 TPa (10 Mbar)

From first-principles total-energy calculations on Hg over a wide volume range, we predict: (i) a pressure-induced bct (β-Hg) to hcp phase transition near 100 GPa (1 Mbar); (ii) a stable, low-temperature hcp structure from 100 GPa to at least 1 TPa (10 Mbar), with a high but increasing c/a ratio approaching a limiting value of 1.83; and (iii) three additional distorted, metastable phases (including α-Hg), all possibly energetically accessible at high temperature.     

微区Raman光谱在TiO_2高压结构相变研究中的应用

本文以金红石单晶TiO2和锐钛矿多晶TiO2为研究对象,应用金刚石小压机和原位拉曼光谱测量技术,系统研究了室温高压下TiO2的结构相变。原位拉曼测量表明,金红石单晶TiO2在压力达到12.91GPa时开始发生由金红石结构向斜锆石结构(MI)的相变,当压力达到14.16 GPa时,相变完成;继续加压到21.65 GPa,没有发现进一步的相变;卸压时由斜锆石结构转变为PbO2结构,相变发生在大约7.11 GPa处。锐钛矿多晶TiO2在压力达到4.26 GPa时开始向PbO2结构转变,当压力达到8.34 GPa时相变完成;继续加压到12.94 GPa,样品开始发生由PbO2结构向斜锆石结构的相变,当压力达到18.74 GPa时相变完成;继续加压到21.39 GPa,没有发现进一步的相变;卸压时也由斜锆石结构转变为PbO2结构,起始相变压力点应高于8 GPa。     

Experimental constraints on the phase diagram of elemental zirconium

The phase diagram of zirconium metal has been studied using synchrotron X-ray diffraction and time-of-flight neutron scattering at temperatures and pressures up to 1273 K and 17 GPa. The equilibrium phase boundary of the α-ω transition has a dT/dP slope of 473 K/GPa, and the extrapolated transition pressure at ambient temperature is located at 3.4 GPa. For the ω-β transition, the phase boundary has a negative dT/dP slope of 15.5 K/GPa between 6.4 and 15.3 GPa, which is substantially smaller than a previously reported value of −39±5 K/GPa in the pressure range of 32-35 GPa. This difference indicates a significant curvature of the phase boundary between 15.3 and 35 GPa. The α-ω-β triple point was estimated to be at 4.9 GPa and 953 K, which is comparable to previous results obtained from a differential thermal analysis. Except for the three known crystalline forms, the β phase of zirconium metal was found to possess an extraordinary glass forming ability at pressures between 6.4 and 8.6 GPa. This transformation leads to a limited stability field for the β phase in the pressure range of 6-16 GPa and to complications of high-temperature portion of phase diagram for zirconium metal.     

Phase diagram of RDX (hexahydro-1,3,5-trinitro-s-triazine) at high pressures and temperatures

Abstract

The phase diagram of RDX-h₆ (hexahydro-1,3,5-trinito-s-triazine) and RDX-d₆ has been studied by Raman spectroscopy to more than 13 GPa at 295 K and 7.5 GPa between 150 and 450 K. Two stable high pressure phases have been found. γ-RDX or RDX-III forms from α-RDX above 3.8 GPa below 380 K. β-RDX forms when α- or γ-RDX are heated, can be retained metastably at low temperatues, and may be related to a very unstable form occasionally recovered at ambient pressure. Deuterium isotopic substitution and shear increase the temperature where β-RDX begins to form on heating.     

高压下α-石英和柯石英的相变行为

利用金刚石压腔和同步辐射X射线衍射技术,对α-石英和柯石英在常温高压下的相变行为进行了研究。实验结果表明:α-石英在约23 GPa开始发生结构相变,在约44 GPa相变完成,直至59 GPa仍能观察到结晶态;柯石英在约22 GPa转变为柯石英-Ⅱ相,高于36 GPa时,继续发生结构转变,直至59 GPa仍有结晶态;氖气和氩气所提供的不同静水压条件对α-石英和柯石英的高压相变行为影响不大。实验结果为进一步厘清二氧化硅物相的压致相变行为和相变机制提供了实验支撑。     

Temperature dependence of bismuth structures under high pressure

It is unclear whether there is a liquid-liquid phase transition or not in the bismuth melt at high temperature and high pressure. If so, it will be necessary to confirm the boundary of the liquid-liquid phase transition and clarify whether it is a first-order phase transition. Here, based on x-ray absorption spectra and simulations, the temperature dependence of bismuth structures is investigated under different pressures. According to the similarity of characteristic peaks of x-ray absorption near edge structure (XANES) spectra, we estimate the possible temperature ranges of liquid-liquid phase transition to be 779-799 K at 2.74 GPa and 859-879 K at 2.78 GPa, 809-819 K at 3.38 GPa and 829-839 K at 3.39 GPa and 729-739 K at 4.78 GPa. Using ab initio molecular dynamics (AIMD) simulations, we obtain the stable structures of the bismuth melt at different temperatures and pressures, and calculated their electronic structures. Meanwhile, two stable phases (phase III-like and phase IV-like) of bismuth melts are obtained from different initial phases of bismuth solids (phase III and phase IV) under the same condition (3.20 GPa and 800 K). Assuming that the bismuth melt undergoes a phase transition from IV-like to III-like between 809 K and 819 K at 3.38 GPa, the calculated electronic structures are consistent with the XANES spectra, which provides a possible explanation for the first-order liquid-liquid phase transition.     

Pressure-induced phase transitions in the Cd-Yb periodic approximant to a quasicrystal

The phase study of a Cd-Yb 1/1 approximant crystal over a wide pressure and temperature range is crucial for the comparison study between periodic and quasiperiodic crystals. The Cd(4) tetrahedra, the most inner part of the atomic clusters, exhibited various structural ordering in the orientation sensitive to pressure and temperature. Five ordered phases appeared in a P-T span up to 5.2 GPa and down to 10 K. The propagation direction of ordering alternated from [110] to <111> to at about 1.0 GPa and again to [110] at 3.5-4.3 GPa. The primarily ordered phases that appeared by cooling to 210-250 K between 1.0-5.2 GPa further transformed to finely ordered ones at 120-155 K. Besides the original short-range type interaction, a long-range type interaction was likely developed under pressure to lead to the primary ordering of Cd(4) tetrahedra. Coexistence of these interactions is responsible for the complicated phase behavior.     

Der Einfluß von Gitterstörungen auf die Supraleitung von Quecksilber

The variation of the transition temperature with residual resistance and the longitudinal critical magnetic field was measured on wires of α-Hg, cold worked at 4,2 °K. No transformation intoβ-Hg during cold working was found. An order of magnitude value was obtained for the anisotropy parameter 〈a²〉≈0,005. The continuous decrease of the transition temperature and the increased critical fields are discussed in terms of the low Debye-temperature of Hg.     

Predictions of pressure-induced structural transition,mechanical and thermodynamic properties of α-and β-Si₃N₄ ceramics:ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4.The ground-state parameters accord quite well with the experimental data.Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K.The α→β phase transformation would not occur in a pressure range of 0-40 GPa and a temperature range of 0-300 K.Actually,the α→β transition occurs at 1600 K and 7.98 GPa.For α-and β-Si3N4,the c axes are slightly more incompressible than the a axes.We conclude that β-Si3N4 is a hard material and ductile in nature.On the other hand,β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0-10 GPa.Besides,the thermodynamic properties such as entropy,heat capacity,and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures.Significant features in these properties are observed at high temperature.The calculated results are in good agreement with available experimental data and previous theoretical values.Many fundamental solid-state properties are reported at high pressure and high temperature.Therefore,our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

Phase transformations in the manganese hydride

Abstract

Pure fcc phase of manganese hydride has been synthesized at high temperature from α-Mn and the H₂ gas compressed to 1.2 GPa. This fcc phase transforms into the hcp modification at 6 GPa and 298K.     

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.     

压力高达27 GPa下天然奥长石的XRD分析

在室温高达27 GPa压力下对天然奥长石(Na_0.86K_0.02Ca_0.12Mg_0.01(Fe_0.01Al_1.12Si_2.87O₈))粉晶进行了原位同步辐射X光衍射(XRD)测量,获得了样品的状态方程。实验数据表明随着压力增大奥长石样品在大约3.5 GPa发生了三斜向单斜的相变(P1→C2)和在大约10.0 GPa发生了单斜对称相变(C2→C2/m)。样品三个相的体模量计算值分别为K₀=73.8 GPa (K′=10.98), K_(C2)=124 GPa (K′=1.05) 和K_(C2/m)=272 GPa (K′=0.625)。样品的元素组成影响其T-O-T 键角的刚度、M-O键的强度和Si-O-Al键角的弯曲,从而导致奥长石样品在高压行为的特殊变化。三斜相的奥长石晶胞压缩性具明显的各向异性。实验结果表明在冷俯冲带奥长石可能是碱金属和碱土金属深循环的载体。     

Predictions of pressure-induced structural transition, mechanical and thermodynamic properties of α-and β-Si3N4 ceramics: ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4.The ground-state parameters accord quite well with the experimental data.Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K.The α→β phase transformation would not occur in a pressure range of 0-40 GPa and a temperature range of 0-300 K.Actually,the α→β transition occurs at 1600 K and 7.98 GPa.For α-and β-Si3N4,the c axes are slightly more incompressible than the a axes.We conclude that β-Si3N4 is a hard material and ductile in nature.On the other hand,β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0-10 GPa.Besides,the thermodynamic properties such as entropy,heat capacity,and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures.Significant features in these properties are observed at high temperature.The calculated results are in good agreement with available experimental data and previous theoretical values.Many fundamental solid-state properties are reported at high pressure and high temperature.Therefore,our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

与Al发生扩散反应的非晶(Fe0.99Mo0.01)78Si9B13晶化

 高压下与Al发生扩散反应的非晶(Fe_0.99Mo_0.01)₇₈Si₉B₁₃（FMSB）的晶化产物与纯FMSB的不同。与Al反应的FMSB非晶在3.0~5.0 GPa、780~900 K热处理时,晶化为α-Fe(Al)和次亚稳非晶合金;在这一压力范围以外,720~900 K热处理时,晶化为α-Fe(Si)、Fe₃B或Fe₂B。与Al发生反应的FMSB非晶可能通过与Al的扩散反应在Al/FMSB界面开始晶化。压力和温度对晶化过程的影响主要是由于α-Fe固溶体的Gibbs自由能随压力、温度和Al含量的变化。     

Effect of shear strain on the α-ε phase transition of iron: a new approach in the rotational diamond anvil cell

The effect of shear strain on the iron α-ε phase transformation has been studied using a rotational diamond anvil cell (RDAC). The initial transition is observed to take place at the reduced pressure of 10.8?GPa under pressure and shear operation. Complete phase transformation was observed at 15.4?GPa. The rotation of an anvil causes limited pressure elevation and makes the pressure distribution symmetric in the sample chamber before the phase transition. However, it causes a significant pressure increase at the centre of the sample and brings about a large pressure gradient during the phase transformation. The resistance to the phase interface motion is enhanced due to strain hardening during the pressure and shear operations on iron and this further increases the transition pressure. The work of macroscopic shear stress and the work of the pressure and shear stress at the defect tips account for the pressure reduction of the iron phase transition.     

In situ X-Ray study of thermal expansion and phase transition of iron at multimegabar pressure

The density of varepsilon-iron has been calculated at pressures and temperatures up to 300 GPa and 1300 K, respectively. We observe varepsilon to beta phase transition at pressures between 135 and 300 GPa and temperature above 1350 K; the pattern can be interpreted in terms of double hexagonal close-packed structure. The density calculated at high pressure and temperature (330-360 GPa and 5000-7000 K) closely matches with preliminary reference Earth model density, thereby imposing constraint on the composition of the Earth's inner core.     

Simultaneous electrical and X-ray diffraction studies on neodymium metal to 152 GPa

Using designer diamond anvils and angle dispersive X-ray diffraction technique at a synchrotron source, we have performed simultaneous electrical and structural studies on neodymium metal to 152 GPa in a diamond anvil cell. Four-probe electrical resistance measurement shows a 38% decrease in the electrical resistivity, associated with the delocalization of the 4f-shell electrons, starting at 100 GPa up to a final pressure of 152 GPa. The continuous decrease in electrical resistivity is consistent with the observation of a gradual phase transition to α-U structure in this pressure range. The (1 1 1) diffraction peak of α-U structure first appears at 100 GPa and increases in intensity with increasing pressure to 152 GPa. This increase in intensity is attributed to an increasing volume fraction of α-U phase and an increase in structural y-parameter from 0.07 at 118 GPa to 0.095 at 152 GPa. In contrast to the abrupt pressure-induced f-electron transition seen in cerium and praseodymium, the continuous evolution of α-U structure and electrical resistivity in neodymium confirms the gradual nature of 4f delocalization process in this element.     

High-pressure study of topological semimetals XCd2Sb2 (X = Eu and Yb)

Topological materials have aroused great interest in recent years, especially when magnetism is involved. Pressure can effectively tune the topological states and possibly induce superconductivity. Here we report the high-pressure study of topological semimetals $X$Cd$_{2}$Sb$_{2}$ ($X = {\rm Eu} $ and Yb), which have the same crystal structure. In antiferromagnetic (AFM) Weyl semimetal EuCd$_{2}$Sb$_{2}$, the Néel temperature (${T}_{\rm N}$) increases from 7.4 K at ambient pressure to 50.9 K at 14.9 GPa. When pressure is above 14.9 GPa, the AFM peak of resistance disappears, indicating a non-magnetic state. In paramagnetic Dirac semimetal candidate YbCd$_{2}$Sb$_{2}$, pressure-induced superconductivity appears at 1.94 GPa, then ${ T}_{\rm c}$ reaches to a maximum of 1.67 K at 5.22 GPa and drops to zero at about 30 GPa, displaying a dome-shaped temperature-pressure phase diagram. High-pressure x-ray diffraction measurement demonstrates that a crystalline-to-amorphous phase transition occurs at about 16 GPa in YbCd$_{2}$Sb$_{2}$, revealing the robustness of pressure-induced superconductivity against structural instability. Similar structural phase transition may also occur in EuCd$_{2}$Sb$_{2}$, causing the disappearance of magnetism. Our results show that $X$Cd$_{2}$Sb$_{2}$ ($X = {\rm Eu}$ and Yb) is a novel platform for exploring the interplay among magnetism, topology, and superconductivity.     

Bonding in the superionic phase of water

The predicted superionic phase of water is investigated via ab initio molecular dynamics at densities of 2.0--3.0 g/cc (34-115 GPa) along the 2000 K isotherm. We find that extremely rapid (superionic) diffusion of protons occurs in a fluid phase at pressures between 34 and 58 GPa. A transition to a stable body-centered cubic O lattice with superionic proton conductivity is observed between 70 and 75 GPa, a much higher pressure than suggested in prior work. We find that all molecular species at pressures greater than 75 GPa are too short lived to be classified as bound states. Up to 95 GPa, we find a solid superionic phase characterized by covalent O-H bonding. Above 95 GPa, a transient network phase is found characterized by symmetric O-H hydrogen bonding with nearly 50% covalent character. In addition, we describe a metastable superionic phase with quenched O disorder.     

α-LiIO3的等温压缩和高温高压下的相变

用金刚石压砧高压X射线衍射技术研究了α-LilO₃在室温高压下的压缩行为,压力达23.0GP_a。观察到晶格压缩的各向异性,其c/a轴比以-6.187×10^-3/GP_a的速率减小。得到其常压下的体弹模量B₀=39.2GP_a,体弹模量对压力的一阶导数B＇₀=3.787。α-LiIO₃在高温高压下转变成四方结构,与淬火卸压所得的ε-LiIO₃结构一致。 关键词：