Phase transitions in uranium dioxide at high pressures and temperatures

The melting curve is plotted for uranium dioxide with fluorite structure in a pressure range from ?2.5 to +100 GPa. This curve has a peak at the point 3348 K, 6 GPa, and has a negative derivative at high pressures. The pressure corresponding to a polymorphic transition of uranium dioxide (37 GPa) at a temperature of 1015 K is determined. The slope of the equilibrium curve of the polymorphic transition in UO₂ in the temperature range 300–1000 K is ? 56 K/GPa.     

Graphitization of activated carbon under high pressures and high temperatures

Activated carbon was treated at 5.0 GPa up to 1600 ^°C and the structural evolution in the graphitization process was investigated. The graphitization temperature is reduced to 1200 ^°C at 5 GPa, as reflected by x-ray diffraction patterns. Honeycomb-like structures come into being in the high-pressure sintering temperature range of 1000–1100 ^°C and slice-like structures appear after graphitization. Raman frequency and half width drop drastically near the graphitization temperature, and the appearance of D and D′ lines indicates there are still some disorder structures in the graphitized activated carbon.     

Effect of carbon materials on the graphite-diamond phase transition at high pressures and temperatures

Experimental data are used in an attempt to unravel the mechanism underlying the effect of modification of a graphite blend by fullerenes on the diamond synthesis at high pressures and temperatures in the presence of metal catalysts. Diamonds have been synthesized under different conditions in a wide range of temperatures and at different pressures, and the effects of blend modification by fullerenes and by addition of natural microcrystalline diamonds to a blend on the diamond synthesis at high pressures and temperatures have been compared.     

Polyhedral carbon nanoparticles at high pressures

JETP Letters - The solid-phase transformations of polyhedral nanoparticles at a pressure of 8.0 GPa and various temperatures have been investigated by X-ray diffraction, small-angle X-ray...     

Polyhedral carbon nanoparticles at high pressures

The solid-phase transformations of polyhedral nanoparticles at a pressure of 8.0 GPa and various temperatures have been investigated by X-ray diffraction, small-angle X-ray scattering, and transmission electron microscopy. It has been found that the graphene layers of the inner cavities of polyhedral particles are transformed into onion-like structures at temperatures above ～1000°C. This transformation gives rise to the formation of hybrid-type sp2 carbon nanoparticles, which combine the outer polyhedral shape with the quasispherical onion-like core. Polyhedral nanoparticles smaller than ～40 nm are completely transformed into onion-like particles at 1600°C.     

Phase transition of ZnS at high pressures and temperatures

The high-pressure behaviour of zinc sulphide, ZnS, has been investigated, using an in situ X-ray powder diffraction technique in a diamond anvil cell, at pressures and temperatures up to 35 GPa and 1000 K, respectively. The pressure-induced phase transition from a zincblende (B3) to a rocksalt (B1) structure was observed. This transition occurred at 13.4 GPa and at room temperature, and a negative dependence on temperature for this transition was confirmed. The transition boundary was determined to be P (GPa) = 14.4 ? 0.0033 × T (K).     

Thermodynamics of ice at high pressures and low temperatures

A new equation of state of ice Ih recently proposed by Feistel and Wagner [J. Phys. Chem. Ref. Data 35 (2006) 1021-1047] is used to study the phenomena related to the equilibrium isentropic compression of an ice-water mixture and dynamic loading of solid ice. New results are presented concerning the properties of the new equation of state, equilibrium solid-liquid phase transitions and Hugoniots of low-temperature (100 K) and temperate (263 K) shock-compressed ice.     

Electrophysical properties of calcium at high pressures and temperatures

Electrical resistivity of two crystal phases of shock-compressed calcium and its melt was measured in a range of high pressures (10–50 GPa) and temperatures (800–1600 K). The thermodynamic equilibrium curves were constructed for different calcium phases and the shape of Hugoniot adiabat was determined in the region where it intersects the equilibrium curves. It is shown that sharp kinks observed earlier in the Hugoniot adiabat in shock experiments were caused not by the jumplike electronic transitions but by the intersections of the adiabat and the phase-equilibrium and melting curves. The electronic spectra of the calcium crystal phases were calculated using the electron-density functional method; the computational results are used to explain the observed behavior of the Ca resistivity under compression.     

Velocity of deflagration combustion at high pressures and temperatures

The article presents additional calculated data on combustion velocity for typical gas mixtures at pressures up to 6000 atm and temperatures up to 4000 K. It was determined that combustion velocity is mainly influenced by initial temperature, and the dependence on pressure is rather low. For fuel-oxygen and air-fuel mixtures in three-dimensional space (pressure-temperature-velocity of deflagration combustion), we have found a single surface of combustion velocities and continuous dependence of flame velocity on initial conditions.     

Dissociation of liquid silica at high pressures and temperatures

Liquid silica at high pressure and temperature is shown to undergo significant structural modifications and profound changes in its electronic properties. Temperature measurements on shock waves in silica at 70-1,000 GPa indicate that the specific heat of liquid rises SiO(2) well above the Dulong-Petit limit, exhibiting a broad peak with temperature that is attributable to the growing structural disorder caused by bond breaking in the melt. The simultaneous sharp rise in optical reflectivity of liquid SiO(2) indicates that such dissociation causes the electrical and therefore thermal conductivities of silica to attain metalliclike values of 1-5 x 10(5) S/m and 24-600 W/m x K, respectively.     

Phonon spectrum and interaction between nanotubes in single-walled carbon nanotube bundles at high pressures and temperatures

The Raman spectra of single-walled carbon nanotubes at temperatures up to 730 K and pressures up to 7 GPa have been measured. The behavior of phonon modes and the interaction between nanotubes in bundles have been studied. It has been found that the temperature shift of the vibrational G mode is completely reversible, whereas the temperature shift of radial breathing modes is partially irreversible and the softening of the modes and narrowing of phonon bands are observed. The temperature shift and softening of radial breathing modes are also observed when samples are irradiated by laser radiation with a power density of 6.5 kW/mm². The dependence of the relative frequency Ω/Ω₀ for G ⁺ and G ^? phonon modes on the relative change A ₀/A in the triangular lattice constant of bundles of nanotubes calculated using the thermal expansion coefficient and compressibility coefficient of nanotube bundles shows that the temperature shift of the G mode is determined by the softening of the C-C bond in nanotubes. An increase in the equilibrium distances between nanotubes at the breaking of random covalent C-C bonds between nanotubes in bundles of nanotubes is in my opinion the main reason for the softening of the radial breathing modes.     

Structure changes in vacancy-rich titanium monoxide at high pressures and high temperatures

Abstract

Powdered samples of TiO_0.82, TiO_1.04 and TiO_1.25 having the cubic rocksalt-type structure with high concentration of vacancies randomly distributed were held at combined conditions of high pressure, ranging from 1 GPa to 8 GPa, and high temperature, ranging from 973 K to 1173 K, and structural changes occurring were investigated by synchrotron radiation diffraction at the conditions and by conventional X-ray diffraction after the samples were brought back to ambient condition. Pressure has been shown to suppress formation of ordered arrangements of vacancies in all the samples and lead to precipitation of a hexagonal δ-Ti₃O₂ in TiO_0.82 and TiO_1.04 and precipitation of a corundum-type Ti₂O₃ in TiO_1.25. Irreversible change in the lattice parameter of the remaining rocksalt-type structure has been observed which is due to partial annihilation of vacancies under pressure.     

Phase equilibria of multicomponent mineral systems at high pressures and high temperatures

Abstract

The substance of the Earth's upper mantle was essentially differentiated in the course of deep-seated magmatic processes. It is for the most part formed by peridotitic as well as pyroxenitic and eclogitic The most deep-seated ones pertain to the garnet-peridotitic facies. Liquidus phase relations between the minerals of primary garnet lherzolite (compositional estimations are given in Refs. 1–3) account for the regularities of the formation, evolution, crystallization of multicomponent silicate magmatic melts and petrogenesis of garnet-peridotitic mantle rocks.     

Analysis of thermoelastic behaviour of MgO at high temperatures and high pressures

The thermoelastic behaviour of MgO has been studied for the temperature range (300-3000 K) under different compressions down to V/V₀=0.3. It has been shown that a comprehensive study of the thermoelastic properties of MgO can be made with the help of the Anderson-Isaak equation for thermal expansivity and the Vinet equation of state taken together. We have estimated the values of thermal expansivity α, isothermal bulk modulus K_T, their variations with pressure and temperature, the Anderson-Gruneisen parameter and the change in entropy with compression for MgO along isotherms at different temperatures. The results have been discussed and compared with the corresponding values reported in the recent literature.     

Structural and magnetic properties of chromium dioxide at high pressures

Ab initio calculations were performed on CrO₂ to study its behavior and possible similarity to silica under high pressures. At the rutile→CaCl₂-type phase transition, the lattice constants, cell volume and total energy change continuously, indicating the second-order nature of the phase transition, consistent with the experimental observations. The current calculations have demonstrated that the rutile→CaCl₂-type phase transition is driven by the softening of the Raman active B_1g mode, weakly coupling with the elastic shear modulus C_s. Further phase transitions of CrO₂ to denser packed phases of α-PbO₂-type and pyrite have been well predicted by total energy calculations. Our electronic calculations revealed that CrO₂ is still a half-metallic ferromagnet up to pressure of 95 GPa. The present results confirm the analogy of the phase sequence between silica and CrO₂ at high pressures.     

高温高压下稠密氢的离解与电离

应用自恰变分自由能模型描述了在化学平衡下,H2,H,H ,e构成地混合物在天体物理和高压实验中遇到情形下的各种相互作用及压力与温度效应引起地离解和电离现象.目前的模型预测了在压力电离区存在一热力学不稳定状态,当温度Tc=15.5 kK,压力Pc=58.3 GPa和密度ρc=0.3226 g/cm3时发生等离子体相变,此理论预测结果与各种模型计算结果进行了比较分析.     

Electric strength of rocks at a pulsed voltage under high pressures at high temperatures

The electric strength of rocks (granite, limestone, and sandstone) for the first time has been measured under the simultaneous effect of the pressure up to 35 MPa and temperature up to 120°C in the system of rod-rod electrodes arranged on one sample surface and point-plane electrodes in the liquid medium of a drilling agent. With the simultaneous increase in pressure and temperature, the electric strength of rocks for point-plane electrodes continuously increases (especially rapidly in the pressure range of 10–24 MPa and temperature range of 35–85°C), while for rod-rod electrodes arranged on the same sample surface, the electric strength varies with a maximum at pressures of 5–12 MPa and temperatures 20–35°C.     

Corrosion of manganese in sulfur dioxide at high temperatures

The reaction of manganese with sulfur dioxide at 0.1 MPa at 973–1173 K was studied. The composition and morphology of the scales were investigated by scanning electron microscopy (SEM) and various of X-ray analysis techniques. Transport phenomena occurring in the growing scales were studied by means of radiotracer techniques using sulfur dioxide labeled with the radioactive isotope of sulfur, ³⁵S. The kinetics of the process was measured by means of the gravimetric method. After an initial stage (not examined), the reaction exhibits two subsequent parabolic stages. The scales were mainly composed of oxides with some sulfide, even though the sulfide is unstable in the reaction conditions. The dominant transport process is the outward diffusion of manganese. Some inward transport of SO₂/S₂ was also observed. The sulfide present next to the metallic core is formed during the very initial stage of the reaction in mixture with the oxide. The process initially occurs mainly by means of reaction of manganese with sulfur dioxide. Further growth of this mixed layer proceeds by means of an inward transport of SO₂/S₂ molecules.     

Electrical conductivity of MgCO3 at high pressures and high temperatures

The electrical conductivity of polycrystalline magnesite (MgCO₃) was measured at 3-6 GPa at high temperatures using complex impedance spectroscopy in a multi-anvil high-pressure apparatus. The electrical conductivity increased with increasing pressure. The activation enthalpy calculated in the temperature range 650-1000 K also increased with increasing pressure. The effect of pressure was interpreted as being the activation volume in the Arrhenius equation, and the fitted data gave an activation energy and volume of 1.76±0.03 eV and −3.95±0.78 cm³/mole, respectively. The negative activation volume and relatively large activation energy observed in this study suggests that the hopping of large polarons is the dominant mechanism for the electrical conductivity over the pressure and temperature range investigated.