高温高压下过渡金属Ru的结构相变

采用基于密度泛函理论的第一性原理和准简谐晶格动力学方法对Ru的六角密排 (hcp)、面心立方 (fcc)、体心四方 (bct) 和体心立方 (bcc) 结构的磁性、晶格结构稳定性和高温高压下的相变进行了系统的研究. 计算获得了各相结构的磁性基态及其稳定性范围, 结果表明: 零温下在计算的压力范围内, NM-hcp 结构是Ru最稳定的结构, 压力的单独作用下并没有相变的发生; NM-fcc结构是Ru的亚稳定结构, 而NM-bcc和FM-bct结构在动力学上并不稳定. 高温高压下Ru将发生从NM-hcp到NM-fcc结构的相变, 并给出了Ru的温度压力相图. 关键词： 相变 晶格稳定性 磁性 第一性原理     

Thermodynamic properties and plasma phase transition of xenon at high pressure and high temperature

By using recent Padé approximations for the Coulombic contribution and hard-core, Van der Waals and polarisation approximations for the atomic contribution, the thermodynamic functions for the nonideal xenon plasma are constructed. These formulae cover a large range of pressure and temperature. Single ionisation is studied by minimising the free energy with respect to the particle numbers. A second critical point is predicted. The coexistence line for the corresponding first order phase transition (weakly ionised plasma - strongly ionised plasma), the lines indicating the soft transition to a higher degree of ionisation at overcritical temperatures, as well as the border of the coexistence area are presented. The influence of the different interactions on the critical data is discussed.     

The Lindemann melting parameter for argon at high pressure

Elastic constant measurements in solidified argon near the melting temperature have been made for reduced volumes corresponding to melting temperatures from 123 to 206 K. Derived values of the Debye temperature in the limit T → T_m, allowed the Lindemann parameter to be determined, showing that within experimental error, the parameter is constant along that portion of the melting line.     

Theoretical melting curves for cubic solids at high pressure

The Lindemann law, the fourth-order anharmonic equation of state and a model for the volume dependence of the Grüneisen coefficient in cubic crystals are used to derive temperature-strain-pressure relations at melting. The relations depend for their application on knowing the values of fourth-order elastic parameters which are not measured experimentally. It is shown that these values can be estimated from melting data at low pressure. A comparative study of the results with previous determinations obtained from shock-wave data is given for copper, silver and gold. Finally, the theoretical fourth-order melting curves of the three selected metals are calculated using both the Lagrangian and Eulerian strain measures.     

Hardness of materials at high temperature and high pressure

The intrinsic character of the correlation between hardness and thermodynamic properties of solids has been established. The proposed thermodynamic model of hardness allows one to easily estimate hardness and bulk moduli of known or even hypothetical solids from the data on Gibbs energy of atomization of the elements or on the enthalpy at the melting point. The correctness of this approach is illustrated by an example of the recently synthesized superhard diamond-like BC₅ and orthorhombic modification of boron, γ-B₂₈. The pressure and/or temperature dependences of hardness were calculated for a number of hard and superhard phases, i.e. diamond, cBN, B₆O, B₄C, SiC, Al₂O₃, β-B₂O₃ and β-rh boron. Excellent agreement between experimental and calculated values is observed for temperature dependences of Vickers and Knoop hardness. In addition, the model predicts that some materials can become harder than diamond at pressures in the megabar range.     

New phase transition of solid bromine under high pressure

Solid bromine has been studied by x-ray absorption spectroscopy experiments up to a maximum pressure of 75 GPa. The data analysis of the extended fine structure reveals that the intramolecular distance first increases, reaching its maximum value at 25+/-5 GPa. From this value the intramolecular distance abruptly begins to decrease evidencing a nonpreviously observed phase transformation taking place at 25+/-5 GPa. A maximum variation of 0.08 A is observed at 65+/-5 GPa where again a phase transition occurs. This last transformation could correspond with the recently observed change to an incommensurate modulated phase. We discuss the possible generalization of the observed new phase transition at 25+/-5 GPa to the case of the other halogens.     

Micro-raman at very high pressure and variable temperature

Abstract

We have designed a mechanical coupling between a spectrometer and a cryostat which allows the use of a microoptical system placed at the entrance of the spectrometer. Micro-Raman investigations are performed with a membrane diamond anvil cell placed inside the cryostat. The capability of this setup is illustrated with results obtained on benzene at 10 K up to 33 GPa.     

高温高压下方解石相转变的拉曼光谱原位实验研究

用热液金刚石压腔装置结合拉曼光谱技术研究了高温高压下方解石的相变过程及拉曼光谱特征。结果表明:常温条件下,体系压力增至1 666和2 127 MPa时,方解石的拉曼特征峰155cm-1消失,1 087cm-1峰分裂为1 083和1 090cm-1两个谱峰、282cm-1峰突然降至231cm-1,证明其转变为方解石-Ⅱ和方解石-Ⅲ。在起始压力为2 761MPa和低于171℃的升温过程中,方解石-Ⅲ的拉曼散射的各个特征振动峰没有变化。当温度达到171℃,方解石晶体完全变成不透明状,其对称伸缩振动峰1 087cm-1、面内弯曲振动峰713cm-1和晶格振动峰155和282cm-1均发生突变,说明方解石-Ⅲ相变生成一种碳酸钙新相。体系降至常温,该新相一直保持稳定不变,表明高温高压下方解石向碳酸钙新相的转变过程是不可逆的。方解石-Ⅲ与碳酸钙新相之间的相变线方程为P(MPa)=9.09.T(℃)+1 880。碳酸钙新相的对称伸缩振动峰(ν1 087)随压力、温度的变化率分别为dν/dP=5.1(cm-1.GPa-1),dν/dT=-0.055 3(cm-1.℃-1)。     

Phase transitions of sulfur at high pressure: Influence of temperature and pressure environment

Abstract

Phase transitions of orthorhombic sulfur were investigated above 10 GPa by Raman spectroscopy using red light excitation. Transitions into several phases that have been reported in previous studies using green light excitation, are confirmed. The phase behaviour is observed to depend strongly on the preparation method. In the presence of a pressure transmitting medium (methanol/ethanol, 4:1), a sequence of phases α-S₈ → [intermediate phase (“ip”) + S₆] → [S₆ + high pressure-low temperature phase (“hplt”)] is described and characterized. Without the use of a pressure transmitting medium, the phase sequence α-S₈ → [“ip” + “hplt”] + “hplt” is observed. In addition, contributions of amorphous sulfur are detected around 10 GPa, i.e. at pressures below the transformation of α-S₈ into the above-mentioned phases. Characteristic Raman spectra of the different phases are extracted and documented over a wide pressure range.     

高温高压下爆轰产物分子间相互作用的研究

给出了一种由分子流体的冲击Hugoniot实验数据确定原分子之间和离解产物分子、原子相互间作用势参数的方法. 在较低压强下,采用Ross硬球微扰理论软球修正模型确定原分子之间的相互作用势参数;在较高压强下,采用基于统计物理的化学平衡方法来确定分子离解后的分子和原子之间的相互作用势参数. 与传统的由对应状态定律确定势函数参数的方法相比,所得到的势函数参数在很大的压强范围内都能较好地描述冲击实验. 关键词： 高温高压 化学平衡 冲击Hugoniot实验     

高温高压下爆轰产物中不同种分子间的相互作用

给出了一种由特殊炸药的爆轰参数确定不同种分子间势函数参数的方法:由基于统计物理的爆轰产物物态方程程序类CHEQ,计算炸药RX-23-AB,HNB和PETN的爆轰参数,反推分子间的相互作用.给出了炸药主要爆轰产物H₂O,CO₂和N₂之间的非理想混合修正系数:K_N2-H2O=1.03,k_N2-CO2=1.035,k_H2O-CO2=0.96,将本文确定的不同种分子间势函数参数用于计算炸药PBX9404的超高压雨贡纽,获得了与实验一致的结果,验证了方法和参数的合理性.     

Phase transition of NaGaO2 at high pressure and high temperature

This work presents a comprehensive study on phase transition in NaGaO₂ under high pressure and temperature (P–T) conditions. X-ray diffraction (XRD) was used to identify the phase composition of the recovered samples. Our results revealed that NaGaO₂ could undergo a structural phase transition from orthorhombic $\beta$- NaGaO₂ to hexagonal $\alpha$- NaGaO₂ under high pressure and temperature. The pressure–temperature phase boundaries of NaGaO₂ were determined up to 5 GPa and 2073 K. The hexagonal $\alpha$- NaGaO₂ sample recovered from higher pressure and temperature exhibited a highly (003) preferred orientation. Besides, a reversible transition from $\alpha$- to $\beta$- NaGaO₂ was observed above 473 K under normal-pressure condition. The high-pressure melting curve of NaGaO₂, for the first time, was measured by using in-situ thermal measurement.     

Chemical transformations of benzene under high pressure and at high temperature

Abstract

In order to understand the chemical transformations of organic compounds composed of aromatic rings under high pressure and at high temperature, we have studied the benzene behavior up to 25 GPa and 550°C by Raman scattering. The chemical transformations and the phase diagram have been established. This point was worth investigating because the phases of benzene before the chemical transformations influence the characteristics of the recovered compound at atmospheric pressure.     

The dehydration kinetics of gypsum at high pressure and high temperature

An in situ dehydration kinetics study of gypsum under water-saturated condition was performed in the temperature and pressure ranges of 383–423?K and 343–1085?MPa by using a hydrothermal diamond anvil cell and Raman spectroscopy. Kinetic analysis shows that the dehydration rate k increases with pressure, suggesting a negative pressure dependence on dehydration rate. The elevation of temperature can contribute to the dehydration. The n values increase with pressure, indicating that the nucleation process becomes slower relative to the growth process. According to the n values of ～1.0, the dehydration of gypsum is dominated by an instantaneous nucleation and diffusion-controlled growth mechanism. The obtained average activation volume ?V is equal to 5.69?cm³/mol and the calculated activation energy E_a and the pre-exponential factor A are 66.9?kJ/mol and 4.66?×?10⁵?s^?1. The activation energy may be dependent upon grain size, shape, temperature and pressure, and surrounding water.     

Crystalline post-quartz phase in silica at high pressure

alpha-quartz, which has been reported to undergo pressure-induced amorphization, was found to transform to a monoclinic, crystalline phase when compressed to 45 GPa at room temperature in a close to hydrostatic, helium pressure medium. The x-ray powder diffraction data obtained could be indexed based on a monoclinic cell, and the intensities are in agreement with a P2(1)/c model structure built up of 3x2 zigzag chains of SiO6 octahedra. This new polymorph of silica, which is metastable under ambient conditions, has been isolated for the first time and is one of several possible competing dense forms containing octahedrally coordinated silicon.