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.     

Thermodynamic properties of OsB under high temperature and high pressure

The energy-volume curves of OsB have been obtained using the first-principles plane-wave ultrasoft-pseudopotential density functional theory (DFT) within the generalized gradient approximation (GGA) and local density approximation (LDA). Using the quasi-harmonic Debye model we first analyze the specific heat, the coefficients of thermal expansion as well as the thermodynamic Grüneisen parameter of OsB in a wide temperature range at high pressure. At temperature 300 K, the coefficients of thermal expansion α_V by LDA and GGA calculations are 1.67×10⁻⁵ 1/K and 2.01×10⁻⁵ 1/K, respectively. The specific heat of OsB at constant pressure (volume) is also calculated. Meanwhile, we find that the Debye temperature of OsB increases monotonically with increasing pressure. The present study leads to a better understanding of how the OsB materials respond to pressure and temperature.     

The conductivity at high fields in films of amorphous niobium dioxide

Amorphous films of NbO_2.00 have been prepared by sputtering solid targets of NbO₂ in an atmosphere of 10% vol. of H and 90% vol. of Ar. Measurements of the conductivity at high electric fields show that the high field conductivity σ(F) can be described by: $\text{σ(}\text{F}\text{) =}\text{σ(0)}\text{Sinh}\text{(}\text{edF}\text{2}\text{kT}\text{)}\text{edF}\text{2}\text{kT}$ where d represents the hopping distance between defect centres having a density of ～ 3 × 10¹⁹cm^?3. Similar behaviour has been observed previously in other transition metal oxides with the defect centres attributed to oxygen vacancies.     

Thermodynamic properties of lithium,sodium, and potassium at high pressure

The Gibbs thermodynamic potential is constructed for Li, Na, and K in the lattice vibration approximation with the aid of the Krasko-Gurskii model pseudopotential. The isothermal modulus of volume elasticity and its pressure derivative are calculated. Compression values are calculated from the equation of state d/d =0. The results obtained agree well with experiment.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 91–97, February, 1978.     

Thermodynamic properties of rhodium at high temperature and pressure by using mean field potential approach

The thermophysical properties of rhodium are studied up to melting temperature by incorporating anharmonic effects due to lattice ions and thermally excited electrons. In order to account anharmonic effects due to lattice vibrations, we have employed mean field potential (MFP) approach and for thermally excited electrons Mermin functional. The local form of the pseudopotential with only one effective adjustable parameter r_c is used to construct MFP and hence vibrational free energy due to ions – F_ion. We have studied equation of state at 300 K and further, to access the applicability of present conjunction scheme, we have also estimated shock-Hugoniot and temperature along principle Hugoniot. We have carried out the study of temperature variation of several thermophysical properties like thermal expansion (β_P), enthalpy (E_H), specific heats at constant pressure and volume (C_P and C_V), specific heats due to lattice ions and thermally excited electrons (C_V^ion and C_V^el, isothermal and adiabatic bulk moduli (B_T and B_s) and thermodynamic Gruneisen parameter (γ_th) in order to examine the inclusion of anharmonic effects in the present study. The computed results are compared with available experimental results measured by using different methods and previously obtained theoretical results using different theoretical philosophy. Our computed results are in good agreement with experimental findings and for some physical quantities better or comparable with other theoretical results. We conclude that local form of the pseudopotential used accounts s-p-d hybridization properly and found to be transferable at extreme environment without changing the values of the parameter. Thus, even the behavior of transition metals having complexity in electronic structure can be well understood with local pseudopotential without any modification in the potential at extreme environment. Looking to the success of present scheme (MFP + pseudopotential) we would like to extend it further for the study of liquid state properties as well as thermophysical properties of d and f block metals.     

Microstructure and oxidation of hot-dip aluminized titanium at high temperature

High-temperature diffusion of a hot-dip aluminized titanium is conducted to study microstructure changes and oxidation behavior of the aluminized titanium. After aluminizing, the titanium substrate is covered by a black layer in which tiny block-shaped TiAl₃ particles are scattered in aluminum matrix. Based on the diffusion experiment results, the thickness of the aluminum diffusion layer at 800 °C increases with diffusion time. However, the aluminum diffusion layer at 900 °C grows and reaches its maximum thickness in 6 h, and then the thickness of the aluminum diffusion layer is reduced with prolonged diffusion time. An inversion of the diffusion layer thickness versus time appears for the aluminized titanium treated at 1000 °C, and the thickness of the diffusion layer keeps declining with diffusion time. The phases present in the outer and middle sublayers are titanium-rich TiAl₃ and equilibrium TiAl₃, respectively. However, the phase in inner sublayer changes from titanium-rich TiAl₃ to TiAl₂ and TiAl as diffusion temperature and time increase. Through energy-dispersive X-ray and X-ray diffraction analysis, the oxides formed in the oxidation process are Al₂O₃ and Al₂TiO₅. Although the oxide scale formed on the surface of the aluminized titanium has an insufficient stability and integrity, the thermal oxidation resistance of the aluminized titanium is still improved by over 5 times compared with that of the pure titanium.     

有限温度下一维Gaudin-Yang模型的热力学性质

本文通过数值求解有限温度下一维均匀费米Gaudin-Yang模型的热力学Bethe-ansatz方程, 研究了此模型的基本性质,得到了在给定的温度或给定的相互作用下, 化学势、相互作用、粒子密度和熵的相互变化图像. 对结果分析发现, 在给定温度和相互作用下, 熵随着化学势的变化有一个量子临界区域.     

Effect of co-dopant on the formation and properties of anatase-type titania solid solutions doped with niobium

The effect of co-dopant M (M=gallium (Ga), aluminum (Al), and scandium (Sc)) on the formation, crystallite growth, optical band gap, photocatalytic activity, and phase stability of anatase-type titanium dioxide solid solutions (Ti_1−2XNb_XM_XO₂) containing the same amount of dopant niobium (Nb) that were directly formed as nanoparticles under mild hydrothermal conditions at 180 °C for 5 h was investigated. The composition range X of the anatase-type solid solutions (Ti_1−2XNb_XM_XO₂) depended on the co-dopant M, i.e., X=0.15-0.20 for M=Ga and Al, and X=0.33 for M=Sc. A remarkable increase in the lattice parameter c₀ was detected in the solid solutions co-doped with M=Sc. The increase in the amount of co-dopant M=Ga and Al enhanced the crystallite growth of the anatase-type solid solutions under the hydrothermal conditions. The photocatalytic activity of the solid solutions (Ti_0.80Nb_0.10M_0.10O₂) co-doped with M=Sc, Ga, and Al increased in that order. The co-dopant M=Ga promoted the anatase-to-rutile phase transformation of the solid solutions at lower temperature.     

Thermodynamic properties of Fe-Ni solid solutions studied by Fe Mössbauer spectroscopy

The room temperature Mössbauer spectra of ⁵⁷Fe were measured for Ni_1−xFe_x solid solutions with x in the range 0.01≤x≤0.10. The obtained data were analysed in terms of short range order parameter (SRO) and the binding energy E_b between two iron atoms in the studied materials using the extended Hrynkiewicz-Królas idea. It was found that the binding energy is positive or Fe atoms interact repulsively. The extrapolated value of E_b for x=0 was used for computation of enthalpy of solution of Fe in Ni. Finally the values of enthalpies of solution were used to predict the mixing enthalpy curve for the Fe-Ni solid solutions. The results were compared with corresponding value given in the literature, which was calculated theoretically using DFT techniques, as well as with the value obtained from experimental calorimetric data and resulting from the cellular atomic model of alloys by Miedema.     

High temperature thermodynamics of solutions of oxygen in vanadium,niobium and tantalum

The Tian-Calvet microcalorimetric method has been applied to the determination at 1323 K of ΔH(O₂), the partial molar enthalpy of mixing of oxygen in vanadium, niobium and tantalum. The present results are in good agreement with earlier studies using e.m.f. techniques. Nevertheless in the first two solutions, ΔH(O₂) has been found somewhat more negative than previously reported. The partial molar entropies of mixing have been recalculated. The low values of the excess entropies are explained by a strong increase of the Debye temperature and a decrease of the electronic density of states at the Fermi level as the oxygen content increases.     

Thermodynamic properties and structural stability of thorium dioxide

Using density functional theory (DFT) calculations, we have systematically investigated the thermodynamic properties and structural stabilities of thorium dioxide (ThO(2)). Based on the calculated phonon dispersion curves, we have calculated the thermal expansion coefficient, bulk modulus, and heat capacities at different temperatures for ThO(2) under the quasi-harmonic approximation. All the results are in good agreement with corresponding experiments proving the validity of our methods. Our theoretical studies can aid a clearer understanding of the thermodynamic behaviors of ThO(2) at different temperatures. In addition, we have also studied possible defect formations and diffusion behaviors of helium in ThO(2), to discuss its structural stability. It is found that in intrinsic ThO(2) without any Fermi energy shifts, the interstitial Th(i)(4+) defect rather than oxygen or thorium vacancies, interstitial oxygen, or any kinds of Frenkel pairs, is the most probable to form with an energy release of 1.74 eV. However, after upshifting the Fermi energy, the formation of the other defects also becomes possible. Regarding helium diffusion, we find that only through the thorium vacancy can it occur with the small energy barrier of 0.52 eV. Otherwise, helium atoms can hardly incorporate or diffuse in ThO(2). Our results indicate that upward shifting of the Fermi energy of ThO(2) should be prevented to avoid the formation of thorium vacancies so as to avert helium caused damage.     

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.     

Thermodynamic formalism of phase transitions in solid solutions

A thermodynamic theory of ferroelectric and ferroelectric-semiconductor solid solutions is presented with account of the effect of hydrostatic pressure in the cases of sharp as well as diffuse transitions. A number of analytical relations are obtained which allow to estimate the effect of admixture concentration and hydrostatic pressure on dielectric permeability, transition temperature, Curie-Weiss constant, heat capacity, thermal expansion coefficient and other properties of crystals with a ferroelectric subsystem. The theoretical results are compared with the experimental data.     

Thermoelastic properties of minerals at high temperature

The knowledge of elasticity of the minerals is useful for interpreting the structure and composition of the lower mantle and also in seismic studies. The purpose of the present study is to discuss a simple and straightforward method for evaluating thermoelastic properties of minerals at high temperatures. We have extended the Kumar’s formulation by taking into the account the concept of anharmonicity in minerals above the Debye temperature (θ _D). In our present study, we have investigated the thermophysical properties of two minerals (pyrope-rich garnet and MgAl₂O₄) under high temperatures and calculated the second-order elastic constant (C _ij ) and bulk modulus (K _T) of the above minerals, in two cases first by taking Anderson–Gruneisen parameter (δ _T) as temperature-independent and then by treating δ _T as temperature-dependent parameter. The results obtained when δ _T is temperature-dependent are in close agreement with experimental data.     

Synergistic influences of titanium,boron, and oxygen on large-size single-crystal diamond growth at high pressure and high temperature

The synergistic influences of boron, oxygen, and titanium on growing large single-crystal diamonds are studied using different concentrations of B₂O₃ in a solvent-carbon system under 5.5 GPa-5.7 GPa and 1300 ℃-1500 ℃. It is found that the boron atoms are difficult to enter into the crystal when boron and oxygen impurities are doped using B₂O₃ without the addition of Ti atoms. However, high boron content is achieved in the doped diamonds that were synthesized with the addition of Ti. Additionally, boron-oxygen complexes are found on the surface of the crystal, and oxygen-related impurities appear in the crystal interior when Ti atoms are added into the FeNi-C system. The results show that the introduction of Ti atoms into the synthesis cavity can effectively control the number of boron atoms and the number of oxygen atoms in the crystal. This has important scientific significance not only for understanding the synergistic influence of boron, oxygen, and titanium atoms on the growth of diamond in the earth, but also for preparing the high-concentration boron or oxygen containing semiconductor diamond technologies.