5种金属高压熔化曲线的理论计算

利用从头算法确定了基于对势的平均场模型中的未知势参数, 从而确定了势函数, 然后利用得到的势函数构建平均场, 进一步计算了5种金属材料 Al, Cu, Ni, Na, K在熔点处原子振动的自由体积. 计算的结果表明, 熔化曲线上原子振动的自由体积与原子晶胞体积之比是常数这一假设并不普遍适用; 对该假设修正后可以比较准确地计算材料的熔化曲线. 关键词： 高压熔化 自由体积理论     

The melting curve of CaSiO3 perovskite under lower mantle pressures

The high pressure melting curve of CaSiO₃ perovskite is simulated by using the constant temperature and pressure molecular dynamics method combined with effective pair potentials for the first time. The simulated results for the partial radial distribution function all compare well with experiment. The calculated equation of state is very successful in accurately reproducing the recent experimental data over a wide pressure range. The predicted high pressure melting curve is in good agreement with the experimental ones, and the melting curve up to the core–mantle boundary pressure, being very steep at lower pressures, rapidly flattens on increasing pressure. The present results also suggest the validity of the experimental data of Zerr and Boehler.     

A simple model for melting curve maxima

A “shouldered” repulsive inter-atomic potential, in conjunction with a statistical mechanics perturbation theory which treats the fluid and solid phases in a consistent way, leads to a maximum in the (P, T) coexistence curve, in qualitative agreement with the melting curve of Cs.     

Theoretical study of a melting curve for tin

The melting curve of Sn has been calculated using the dislocation-mediated melting model with the `zone-linking method'. The results are in good agreement with the experimental data. According to our calculation, the melting temperature of γ -Sn at zero pressure is about 436~K obtained by the extrapolation of the method from the triple point of Sn. The results show that this calculation method is better than other theoretical methods for predicting the melting curve of polymorphic material Sn.     

Lindemann criterion and the anomalous melting curve of sodium

Recent reports of the melting curve of sodium at high pressure have shown that it has a very steep descent after a maximum of around 1000 K at 31 GPa. This maximum does not occur due to a solid-solid phase transition. According to the Lindemann criterion, this behaviour should be apparent in the evolution of the Debye temperature with pressure. In this work, we have performed an “ab initio” analysis of the behaviour of both the Debye temperature and the elastic constants up to 102 GPa, and find a clear trend at high pressure that should cause a noticeable effect on the melting curve.     

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.     

High-pressure melting curve of nitrogen and the liquid-liquid phase transition

The melting curve of nitrogen was measured up to 71 GPa, a fourfold increase in pressure over previous measurements. The measurements were made using the laser-heated diamond anvil cell and melting was detected in situ by the laser speckle method. The melting temperature rises linearly up to a maximum at 50 GPa and 1920 K, and with increasing pressure suddenly decreases linearly to 1400 K at 71 GPa. This sharp drop in the melting slope (dT/dP) above 50 GPa indicates the appearance of a liquid denser than the solid and of a liquid-liquid phase transition. The sharpness of the changes suggests that the transition is first order and is a liquid-liquid polymer transition. This conclusion is consistent with earlier theoretical studies and experimental evidence that pressure transforms molecular nitrogen into a chainlike polymeric form.     

Pseudocritical point on the melting curve of a metastable phase

The possibility of the existence of a limit to which the melting curve can be extrapolated into the metastable region is discussed. The analysis is made for the example of GaSb, for which the stable and metastable phases of the T-P diagram are known. When the melting curve of the high-pressure modification is extrapolated to low pressures, it crosses the curve of complete instability of the disordered phase at a point k. Since the melting curve is a line of equilibrium between two phases, one of which ceases to exist at the point k because the minimum of the thermodynamic potential that corresponds to this phase becomes degenerate, the melting curve terminates at the point k and further extrapolation of the curve is physically meaningless. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 4, 260–262 (25 August 1997)     

铅的高压状态方程与熔化曲线

基于Gray三相状态方程模型,采用GRIZZLY的Grüneisen系数模型,对铅的冲击雨贡纽线、等温压缩线、等熵压缩线和熔化曲线进行了系统计算,优化参数,获得与实验数据一致的冲击雨贡纽线、等温压缩线与等熵压缩线,计算所得熔化温度线与X射线衍射实验结果吻合得很好。     

High-pressure differential thermal analysis measurements of the melting curve of lithium

The pressure effect on the melting behavior of lithium has been measured by observing the latent heat signatures of melting and freezing using differential thermal analysis (DTA). Samples were repeatedly melted and recrystallized at selected pressures up to 15 GPa in a multianvil press. Despite the weak DTA signals due to small sample sizes at high pressure, the melting and freezing temperatures were clearly determined from the derivatives of the DTA traces. We measured a drop in the melting temperature between 9 and 12 GPa, yielding a maximum at 10(2) GPa and 245(2) ^°C. This work highlights both the successes and failures of recent theoretical models for the melting behavior of this and related systems.     

Xenon melting curve to 80 GPa and 5p-d hybridization

Measurements made in a laser heated diamond-anvil cell are reported that extend the melting curve of Xe to 80 GPa and 3350 K. The steep lowering of the melting slope (dT/dP) that occurs near 17 GPa and 2750 K results from the hybridization of the 5p-like valence and 5p-like conduction states with the formation of clusters in the liquid having icosahedral short-range order (ISRO).     

3He melting curve thermometry in a nuclear polarization experiment

Temperature measurement and control are important in brute force polarization experiments. We discuss the installation and use of³He melting curve thermometers in a crystat used to polarize a TiH₂ target. Comparison is made between the melting curve thermometers and the⁶⁰CoCo nuclear orientation thermometer, which is often used in such experiments. The melting curve thermometers provide increased temperature resolution and sensitivity, and were used in a feedback heating system to control temperature to ±5.5 μK at 16.5 mK. The³He melting curve and the⁶⁰CoCo temperature scales are found to agree within 2% at 15 mK. The present status of the melting curve scale and the effect of a magnetic field on melting curve thermometry are also discussed.     

Dynamic loading of solids with a negative slope of the melting curve

The results of experiments on shock-wave loading of materials distinguished by a negative slope of the melting curve are reported. An anomalous situation is possible, when the material is melted by a shock wave and then a fast transition to the solid phase takes place in the expansion wave. The newly formed phase should be a nanostructural formation of the given element. Experiments confirmed the existence of the transition from the liquid to the solid phase of the nanostructural modification.     

Evidence of maximum in the melting curve of hydrogen at megabar pressures

Hydrogen at high pressures of ∼400 GPa might be in a zero-temperature liquid ground state (N. Ashcroft, J. Phys.: Condens. Matter A 12, 129 (2000), E. G. Brovrnan et al., Sov. Phys. JETP 35, 783 (1972)). If metallic hydrogen is liquid, the melting T _melt(P) line should possess a maximum. Here we report on the experimental evaluation of the melting curve of hydrogen in the megabar pressure range. The melting curve of hydrogen has been shown to reach a maximum with T _melt = 1050 ± 60 K at P = 106 GPa and the melting temperature of hydrogen decreases at higher pressures so that T _melt = 880 ± 50 K at P = 146 GPa. The data were acquired with the aid of a laser heating technique where diamond anvils were not deteriorated by the hot hydrogen. Our experimental observations are in agreement with the theoretical prediction of unusual behavior of the melted hydrogen [S. Bonev et al., Nature 481, 669 (2004)]. The article is published in the original.     

Lindemann''s criterion and the necessary condition for a melting curve maximum

Dielectric and differential microcalorimetry measurements have been realized on the $\text{Bi}{}_{\mathrm{1?x}}\text{Te}{}_{\mathrm{x}}\text{O}{}_{\mathrm{<mtext>3+x</mtext><mtext>2</mtext>}}$ (0,33 ? x ? 0,50) solid solution. A phase transition has been detected. The variation of the transition temperature with the composition has been determined. The low temperature phase, stable at 20°C, has piezoelectric and non-linear optical properties.     

Sound velocity measurements of nuclear-ordered solid 3He along the melting curve

We have measured the temperature dependence of the 10.98 MHz longitudinal sound velocity of solid 3He in the nuclear-ordered U2D2 phase and in the paramagnetic phase along the melting curve. The temperature dependence of the sound was attributed to the contributions from the nuclear spin system and the molar volume change along the melting curve. The sound velocity increased with temperature as T4 in the U2D2 phase and the sound anisotropy due to the exchange interaction was found to be about 10% among single-domain crystals investigated. The average value of the Gruneisen constant of the spin wave velocity in the ordered phase was gamma(c) = 16 and is compared to the calculated value of the multiple-exchange model.     

Molecular dynamics study for the melting curve of MgO at high pressure

Shell-model molecular dynamics method is used to study the melting temperatures of MgO at elevated temperatures and high pressures using interaction potentials. Equations of state for MgO simulated by molecular dynamics are in good agreement with available experimental data. The pressure dependence of the melting curve of MgO has been calculated. The surface melting and superheating are considered in the correction of experimental data and the calculated values, respectively. The results of corrections are compared with those of previous work. The corrected melting temperature of MgO is consistent with corrected experimental measurements. The melting temperature of MgO up to 140GPa is calculated.     

Pressure effects on EXAFS Debye-Waller factor and melting curve of solid krypton

The pressure effects on atomic mean-square displacement, extended X-ray absorption fine structure (EXAFS) Debye-Waller factor and melting temperature of solid krypton have been investigated in within the statistical moment method scheme in quantum statistical mechanics. By assuming the interaction between atoms can be described by Buckingham potential, we performed the numerical calculations for krypton up to pressure 120?GPa. Our calculations show that the atomic mean-square displacement and EXAFS Debye-Waller factor of krypton crystal depend strongly on pressure. They make the robust reduction of the EXAFS peak height. Our results are in good and reasonable agreements with available experimental data. This approach gives us a relatively simple method for qualitatively calculating high-pressure thermo-physical properties of materials. Moreover, it can be used to verify future high-pressure experimental and theoretical works.