The phase diagram of the system ZrO2CaOMgO between 1200°C and 1700°C

Solid state phase relations in the system ZrO₂CaOMgO were investigated at 1700°, 1600°, 1500°, 1400°, 1300° and 1200°C. The most significant equilibrium isotherms are reported and the phase diagram of the system in the 1700° to 1200°C temperature range is proposed.     

First principles search of hard materials within the SiCN ternary system

Starting from C₃N₄ and Si₃N₄ stoichiometries and from the pseudocubic model structure of the former, intermediate phases SiC₂N₄ and Si₂CN₄ are proposed and geometry optimised within density functional built pseudopotential method using both local density (LDA) and generalised gradient approximations (GGA). The ternary compounds are found to be less stable than the two binary systems but the trends in the calculated magnitudes of the bulk moduli B₀ from the fit of the E(V) curves with Birch equation of state: B₀ (SiC₂N₄)=334.5 GPa and B₀ (Si₂CN₄)=270.3 GPa can be interpolated from those of the two extreme compounds: B₀ (C₃N₄)=424.1 GPa and B₀ (Si₃N₄)=219.8 GPa. This translates the chemical role of the substituting element on one hand and allows validating Cohen's semiempirical law relating B₀ to the inverse powers of the average interatomic distances on the other hand. From a mismatch of the chemical bonding in Si(C)NC(Si) chain observed by the electron localisation function (ELF) plot we propose an interpretation for the instability of the intermediate ternary phases. The electronic structure (density of states and band structures) obtained from augmented spherical wave (ASW) calculations of the relaxed structures point to semiconducting behaviour with smaller band gaps for the intermediate phases (∼2 eV, compared with the ∼4 eV gap of binaries).     

Topological transformation of the phase diagram of the lithium nitrate-water-acetonitrile ternary system within the range of −20 to 50°C

Phase equilibria and critical phenomena in the lithium nitrate-water-acetonitrile ternary system were studied by a visual polythermal method within the range of ?20 to 50°C. In this ternary system, the constituent liquid binary system is characterized by phase separation with an upper critical solution temperature. It was found that the ternary system undergoes phase separation at temperatures below 0.7°C. In the phase diagram within the range of ?1.1 to 0.7°C, a closed phase separation region with two critical points was revealed. The temperature of the formation of the critical tie line of the monotectic state the solid phase of which is the crystalline hydrate LiNO₃ · 3H₂O was determined (?18.7°C). Depending on the concentration, lithium nitrate has both salting-in and salting-out effect on aqueous acetonitrile mixtures. The plotted isothermal sections of the temperature-concentration prism of the system at fifteen temperatures showed the pattern of the topological transformation of its phase diagram with varying temperature.     

The Nb-rich part of the NbGa phase diagram

Ten alloys in the composition range 11–40 at.% Ga were produced by a four-stage process that involved both sintering and melting stages. These alloys were heat-treated at temperatures in the range 700–1600 °C until equilibrium was attained. The phases present after heat treatment were studied by means of X-ray diffraction, electron probe microanalysis and light microscopy. From the data obtained, the temperature dependence of the solubility limit of gallium in niobium was determined, the homogeneity range of Nb₃Ga was defined, and the second most niobium-rich compound was identified as oxygen-stabilised Nb₅Ga₃O_x.     

Topological transformation of the phase diagram of a potassium perchlorate-water-tetrahydrofuran ternary system in the temperature range of 40 to 140°C

Phase equilibria and critical phenomena in a potassium perchlorate-water-tetrahydrofuran ternary system are studied by visual polythermal means in the range of 40 to 140°C; the solubility diagram of the liquid subsystem is characterized by the presence of isolated binodal curve. The temperature of formation for the critical node of the monotectic state (107.3°C) and the dependences of the composition that corresponds to the critical points of solubility in the delayering field vs. temperature in the ranges of 70.3 to 107.3°C and 137.1 to 140.2°C are determined. The topological transformation of the investigated ternary system’s phase diagram upon a change in temperature is studied using isothermal sections of the system’s temperature concentration prism, plotted at nine temperatures. It is found that potassium perchlorate has only a salting-in effect on mixtures of water and tetrahydrofuran at temperatures below 107.3°C; at higher temperatures, it has both a salting-in and a salting-out effect, depending on its concentration and the composition of mixed solvent. It is shown that potassium perchlorate’s effect of salting tetrahydrofuran out of aqueous solutions grows slightly with an increase in temperature.     

A study on the phase diagram of AlF3CsF system

Phase relations of the AlF₃CsF system have been investigated by the methods of DTA and XRD with quenching technique. Four compounds were identified: Cs₃AlF₆, CsAlF₄, CsF·2AlF₃ and CsF·3AlF₃. Cs₃AlF₆ melts congruently at 790°C. The first eutectic, E₁, between Cs₃AlF₆ and CsF is located in 10.0 mol% AlF₃ at 654°C. CsF·2AlF₃ and CsF·3AlF₃ melt incongruently at 508° and 653°C, respectively. The second eutectic, E₂, was observed in 42.0 mol% AlF₃ at 471°C. The compound CsAlF₄ formed in the solid eutectic when cooled below 443°C. CsAlF₄ has α and β forms, transformation of which takes place reversibly at 422°C. All phase structures in the system were confirmed by X-ray powder diffraction analysis.     

Phase equilibrium diagram of the system MnCrO

A hypothetical oxygen pressure-composition phase diagram and a projection of the oxygen pressure-temperature-composition diagram on the composition triangle were constructed from phase equilibria in the system MnCrO on the basis of the data available in literature. The temperature-composition phase equilibrium diagram of this same system in air was specified. Isomorphism of solid solutions with spinel and hausmannite structure and their intertransformation was studied. Two chemical compounds, MnCr₂O₄ and Cr₄Mn₂₈O₄₈, are supposed to exist in the system.     

Study and 3D modeling of the phase diagram of the Ag–Ge–Se system

In view of the contradictoriness of the literature data, phase equilibria in the Ag–Ge–Se system were restudied by differential thermal analysis and X-ray powder diffraction analysis. A number of polythermal sections and an isothermal section at room temperature of the phase diagram were constructed, and so was the projection of the liquidus surface. The primary crystallization fields of phases and the types and coordinates of in- and monovariant equilibria were determined. It was shown that, in the system, a single ternary compound, Ag₈GeSe₆, forms, which undergoes congruent melting at 1175 K and a polymorphic transformation at 321 K. The formation of the compounds Ag₂GeSe₃ and Ag₈GeSe₅, which was previously reported in the literature, was not confirmed. Based on the phase diagrams of boundary binary systems and the results of the differential thermal analysis of a number of samples of the ternary system, equations were obtained for calculation and 3D modeling of the liquidus and phase-separation surfaces.     

Thermodynamics of the URuC system

Thermodynamic measurements by the electromotive force method were made on the binary intermetallic phases URu₃ and U₃Ru₅ and on the ternary carbides URu₃C_0.7 and U₂RuC₂ of the URu and the URuC systems between 950 and 1200 K using galvanic cells with CaF₂ single crystal electrolytes: U, UF₃¦CaF₂¦UF₃, URu₃, Ru; U, UF₃¦CaF₂¦UF₃, U₃Ru₅, URu₃; Ru, URu₃, UF₃¦CaF₂¦UF₃, URu₃C_0.7, Ru, C; U, UF₃¦CaF₂¦UF₃, URu₃C_0.7, U₂RuC₂, C. The Gibbs energies of formation of URu₃, U₃Ru₅, URu₃C_0.7 and U₂RuC₂ were evaluated from the measured electromotive force which give ^fΔG^o〈URu₃〉 = −199 100 + 35.9 T J mol^−1fΔG^o〈U₃Ru₅〉 = −398 600 + 43.6 T J mol^−1fΔG^o〈URu₃C_0.7〉 = −192 600 + 2.5 T J mol^−1fΔG^o〈U₂RuC₂〉 = −380 200 + 52.5 T J mol⁻¹ The implications of these thermodynamic data for the behaviour of the fission product ruthenium in irradiated carbide fuels are discussed.     

The vibrational spectra of (CH3)3MCCCCM(CH3)3, with M = C,Si, Ge,or Sn

Infrared spectra from 200 to 4000 cm⁻¹ and Raman spectra from 80 to 4000 cm⁻¹ have been recorded for the molecules (CH₃)₃MCCCCM(CH₃)₃ with M = C, Si, Ge, or Sn. Solid samples and solutions in several solvents have been used. Assignments of the fundamentals were made on the assumption of D_3d symmetry, which proved quite satisfactory. In all, 140 of the 188 spectroscopically-active fundamentals for the four molecules have been assigned.The in-phase CC stretch is 115–135 cm⁻¹ higher than the out-of-phase one. This is in sharp contrast to cumulated double bonds, where the in-phase stretch is roughly half the out-of-phase one. A rationalization of this is given.     

Phase diagram of an iodine-potassium iodide-water-ethanol system at 25°C

Phase equilibriums are studied in the isothermal-isobaric sections of the phase diagram of a fourcomponent iodine-potassium iodide-water-ethanol system at 25°C and atmospheric pressure. The compositions of the solvent at which it exhibits the greatest ability to dissolve iodine are established. It is shown that in all the investigated sections, there is three-phase eutonic equilibrium with potassium iodide and crystalline iodine as the solid phases. It is revealed that in the sections containing 30 and 50% of ethanol, potassium iodide serves as the salting in agent for crystalline iodine, due to the formation of polyiodide complexes of various composition in the studied system.     

The revised phase diagram of the Ca3(PO4)2–YPO4 system. The temperature and concentration range of solid-solution phase fields

A revised version of the Ca₃(PO₄)₂–YPO₄ phase diagram has been proposed on the basis of results obtained by thermal analysis (DTA/DSC/TG) and X-ray diffraction methods. A limited solid solution with the structure of β-Ca₃(PO₄)₂ exists in the system. At 1,100 °C the maximal concentration of YPO₄ in the solid solution is ~15 mass%. The solid-solution phase field exists in the temperature range upto ~1,380 °C. Two high-temperature solid solutions with the structure of α′ and α-Ca₃(PO₄)₂ form in system as well, however only the α phase can be obtained by quenching from high temperatures. The Ca₃Y(PO₄)₃ compound with the structure of eulytite forms in the Ca₃(PO₄)₂–YPO₄ system at temperatures exceeding 1,255 °C and does not show any polymorphic transition.