Phase Relations in the Cu–Sb–O System

The Cu–Sb–O system was studied by x-ray diffraction and thermal analysis between 700 and 1000°C. The compositions of copper antimonates were refined. Sb₂O₄ was found to exist in two polymorphs above 800°C: -Sb₂O₄ (dominant phase) and -Sb₂O₄. The evolution of phase equilibria with increasing temperature was examined. The isothermal sections of the Cu–Sb–O phase diagram were mapped out using new and earlier reported results.     

p–T–x Phase Equilibria in the Cd–Zn–Te System

The p–T–x–y phase equilibria in the Cd–Zn–Te system are analyzed. The p–T and T–x–yprojections of the p–T–x–y phase diagram and a T–x–y isobar (for pressures at which Cd_1–x Zn _x Te_{1 ±} solid solutions sublime congruently in terms of Te) are mapped out. The key features of the sublimation behavior of the solid solution are examined. The p–T projection is studied by static vapor pressure measurements at temperatures from 700 to 1300 K and pressures of up to 101.3 kPa. The p–T sections of the phase diagram are constructed for x = 0.05, 0.10, 0.15, 0.25, 0.50, 0.75, 0.90, and 1. The solid solution containing 35 mol % ZnTe is found to phase-separate at 473 K.     

500°C Section of the Y–Ag–Sb Phase Diagram

The 500°C phase relations in the Y–Ag–Sb system were studied by x-ray diffraction analysis. No dissolution of the third component in binary compounds was detected. The existence of the ternary compound YAgSb₂ was confirmed, and its structure was refined by the Rietveld method (sp. gr. P4/nmm, structure type HfCuSi₂, a= 0.42711(2) nm, c = 1.04968(9) nm, R _i = 0.097, R _p = 0.150).     

Optimization of the Phase Diagram of CeO_2-ZrO_2 System

Revised phase diagram of the CeO2-ZrO2 system is optimized and the lattice stability parameters of CeO2 of various phases as well as solution parameters of phases (liquid, cubic, tetragonal and monoclinic) are simultaneously obtained by using the Kaufman and Nesor's model for describing the ceramic solutions and the Lukas program     

Calculation of Thermodynamic Properties from Phase Diagram of the Pb-Zn System

The formulas for obtaining the interaction parameters of the liquid solution were first deduced from the immiscible phase diagram of binary system. Then. the relationships between activity coefficients and interaction parameters of the binary system were also deduced. Finally, thermodynamic properties of the Pb-Zn system were calculated by using these formulas.     

Phase Equilibria in the Li–W–Mn–O System

An isothermal compositional subsolidus phase equilibrium diagram of the Li–W–Mn–O system is constructed. Possible solid-state transformations in the system at a variable pressure and constant temperature are presented and phase transformations involving melt in temperature and pressure ranges of interest are analyzed.     

Phase Relations in the Reduction of Solid Solutions in the Co–Mn–Ti–O System

The hydrogen reduction of spinel solid solutions in the Co–Mn–Ti–O system was investigated by a static method. Six phase regions were identified in which the gas phase is in equilibrium with various combinations of -Co, TiO₂ (rutile), and solid solutions of variable composition: Co _A Mn _B Ti_{3 – A – B} O₄ (spinel), Co _m Mn_{2 – m} TiO₄ (spinel), Co _N Mn_{1 – N} TiO₃ (ilmenite), and Co _n Mn_{1 – n} O (NaCl). The equilibrium compositions of the solid solutions and the corresponding oxygen partial pressures were determined, and the general trends of the reduction of spinel solid solutions in the Co–Mn–Ti–O system were established.     

600°C Section of the Fe–FeS–NiS–Ni Phase Diagram

The 600°C section of the Fe–FeS–NiS–Ni phase diagram was studied by optical and electron microscopy techniques, x-ray diffraction, and electron probe x-ray microanalysis. The results agree with the most reliable data available in the literature. The solid-solution regions identified are those of (Fe _z Ni_{1 – z} )_{3 ±} S₂(high-temperature heazlewoodite structure), (Fe _z Ni_{1 – z} )S_{1 +} , (Fe _z Ni_{1 – z} )_{9 +} S₈(pentlandite structure), -(Fe,Ni), and -(Fe,Ni). The section also contains seven two-phase and three three-phase regions. The S content of the monosulfide solid solution attains 50.8 at. % at Ni : (Ni + Fe) = 0.6 and 54.0 at. % at Ni : (Ni + Fe) = 0.2. The heazlewoodite solid solution contains up to 26 at. % Fe (at 44.3 at. % S). The highest Ni content of the pentlandite solid solution is 22.5 at. % at 47.5 at. % S and 32.0 at. % at 46.2 at. % S.     

Phase Relations in the SrO–Bi2O3–Fe2O3 System

The phase relations in the composition region SrFeO_{3 –} –Fe₂O₃–BiFeO₃ are studied in air by x-ray diffraction and electron microscopy. The 1000°C phase compatibility diagram is constructed. Sr_{1 – x} Bi _x FeO_{3 –} solid solutions are prepared in the range 0 < x 0.8. Their lattice parameter is found to vary nonlinearly with x. Two new phases were identified: (Sr,Bi)₃Fe₄O _y (tetragonal lattice, a= 3.907(2) Å, c= 27.30(2) Å) and Sr_0.6Bi_0.4FeO_{3 –} (tetragonal lattice,a = 5.555(2) Å, c= 11.848(5) Å).     

Advances in the Experimental Determination of the Uranium–Oxygen Phase Diagram at High Temperature

Due to its complex phase diagram and the employment of UO₂ as a nuclear fuel, the binary system U–O is of great interest both scientific and technological. Numerous experimental and theoretical studies have been carried out in the last 45 years in order to determine the properties of this system, leading to a precise definition of a considerable part of the state diagram in the region ranging from pure uranium to stoichiometric UO₂, and at temperatures lower than 1500 K, up to the oxide U₄O₉. However, due to the poor chemical stability of O–U compounds with high oxygen content at high temperature (O/U > 2, T > 2000 K), an important part of the phase diagram still lacks experimental data. In this work measurements are presented on the melting transition of the stoichiometric and hyperstoichiometric dioxide UO_2+x up to x=0.21, and on the melting point of the higher oxide U₃O₈. These measurements were performed under buffer gas pressures varying between 10 and 250 MPa, using a method based on subsecond laser heating developed to overcome experimental difficulties encountered by previous researchers. Paper presented at the Seventh International Workshop on Subsecond Thermophysics October 6–8, 2004, Orléans, France.     

WDX-Analysis of the New Superconductors RO1−x F x FeAs and Its Consequences on the Electronic Phase Diagram

Polycrystalline samples of RO_1−x F _x FeAs (0≤x≤0.25) (R=La, Sm, Gd) were investigated by wavelength-dispersive X-ray spectroscopy (WDX) in the electron microscope to determine the composition of the samples, in particular the fluorine content. It was found that the measured fluorine content can deviate considerably from the initial weight. In the lanthanum compound LaO_1−x F _x FeAs, we found good agreement mainly for x≥0.05, but for x<0.05 the fluorine hardly goes into the sample. For the samarium compound we measured less than half the fluorine in the sample as initially weighed at all fluorine concentrations. These measured values are taken into account when drawing the electronic phase diagrams of LaO_1−x F _x FeAs and SmO_1−x F _x FeAs. This leads to a more consistent picture of both of the diagrams in comparison to the plot of the initial weight.     

Phase Relations in the Li–V2O5–Cu System at 600°C and Cathodic Properties of Cu x V2O5

The phase relations in the Li–V₂O₅–Cu system at 600°C are studied by x-ray diffraction. The existence of the known vanadium bronzes M _x V₂O₅ (M = Li, Cu) is confirmed, and the composition ranges of the related solid solutions are determined. -Li _x V₂O₅ (0.22 x 0.49) and -Li _x V₂O₅ (0.88 x 1.0) are shown to dissolve Cu, forming Li _x Cu _y V₂O₅ solid solutions with y = 0.72 – 1.48x and y = 0.58 – 0.18x, respectively. Cu _x Li _y V₂O₅ solid solutions (y= 0.51 – 0.76 x) are only obtained from -Cu _x V₂O₅ (0.24 x 0.67). -Li _x V₂O₅ and -Cu _x V₂O₅ form a continuous series of solid solutions. The cathodic properties of Li–V₂O₅–Cu materials in high-temperature pulsed lithium batteries are investigated.     

Phase Relations in the NiFe2O4–NiCr2O4–CuCr2O4System

The phase relations in the NiFe₂O₄–NiCr₂O₄–CuCr₂O₄system were investigated experimentally and theoretically. X-ray diffraction data were used to construct the phase diagram of the system and elucidate the structural mechanisms of the transitions from the cubic spinel structure to the tetragonal (I42d, c/a< 1 and I4₁/amd, c/a> 1) and orthorhombic (Fdd2) structures.     

Thermodynamic Modeling of Phase Equilibria in the U–Zr–N System

Inorganic Materials - A thermodynamic model is proposed for condensed phases in the ternary system U–Zr–N in the range 298–2800 K. The model is based on previously reported models...     

Ion-Conducting Defect Pyrochlore Phases in the K2O–Sb2O3–WO3 System

Potassium tungstate antimonates were prepared by calcining K₂CO₃ + Sb₂O₃ + 2(1 – – )WO₃ mixtures in air. Data on the phase composition of the obtained materials were used to locate the pyrochlore phase region in the Sb₂O _z –W₂O₆ – K₂O composition triangle at 1170 K. The distributions of the constituent ions and lattice defects over the crystallographic positions of space group Fd3m were inferred from structural and gravimetric data. The ac conductivity of the potassium tungstate antimonates was measured from 600 to 1000 K. The conductivity and its activation energy were shown to be correlated with the concentrations of cation (position 16d) and anion (position 8b) defects. The concentration and mobility of K⁺ ions involved in charge transport were determined.     

Phase transformations in the ternary Ag–Ga–Sb system

Phase diagram of the Ag–Ga–Sb ternary system was extrapolated using calculation of phase diagrams (CALPHAD) method. Phase transition temperatures of the alloys with compositions along three vertical sections with constant molar ratios Ga/Sb = 1, Ag/Ga = 1 and Ag/Sb = 1 were measured using differential scanning calorimetry (DSC). Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) was used for identification of phases in equilibrated samples. Experimental results were compared with thermodynamic prediction.     

Phase Diagram and Luminescent Properties of CdTe–MnTe Solid Solutions

The T–x phase diagram of the CdTe–MnTe system is mapped out. The CdTe–MnTe join is shown to be nonpseudobinary. The system contains an extended series of CdTe-based solid solutions (0–71.4 mol % MnTe at 1070 K). At 1070 K, -MnTe dissolves up to 0.3 mol % CdTe. Data are presented on the composition dependences of lattice parameters for the solid solutions studied and the luminescent properties of Cd_{1 – x} Mn _x Te single crystals annealed in cadmium or tellurium vapor.     

Mechanochemical Synthesis and Thermal Behavior of Metastable Mixed Oxides in the CaO–Sb2O3–Bi2O3 System

The phase composition of crystalline mechanochemical synthesis products in the CaO–Sb₂O₃–Bi₂O₃ system was determined. Of the known phases in this system, only three could be prepared mechanochemically: Ca₂Sb₂O₅, CaSb₂O₄, and CaBiO_2.5 (fcc). A new metastable phase, "-Bi₂O₃, with an orthorhombic structure close to that of the high-temperature, fluorite phase -Bi₂O₃, was obtained by mechanical processing at 30°C. A number of new metastable fluorite solid solutions of binary and ternary oxides were obtained as single-phase powders by mechanochemical synthesis. The mechanochemical yield of primary crystalline products was shown to be several times higher than that of secondary products. A broad composition range was revealed in which perovskite and fluorite phases are in mechanochemical equilibrium. The composition dependence of the lattice parameter of the metastable fluorite phase Bi_{2 – x} Sb _x O₃ was found to be the opposite of the one predicted by Vegard's law. Metastable mixed oxides undergo phase transformations during heating (starting at 280°C in the case of the ternary perovskite phase). Bi_{2 – x} Ca _x O_{3 – 0.5x} fluorite solid solutions experience a transformation at 400°C, accompanied by oxygen loss. During heating in air, Sb₂O₃-containing fluorite phases partially stabilize owing to oxidation but, nevertheless, undergo structural transformations above 480°C. The transformation of Sb_{2 – x} Ca _x O_{3 – 0.5x} metastable fluorite solid solutions near 500°C in air is accompanied by the formation of needle-like Sb₂O₃ crystals. A mechanism is proposed for the extremely rapid growth of such crystals: extrusion of the Sb₂O₃ resulting from fluorite decomposition in agglomerates through triple junctions of aggregates and through cracks in the surface layer of agglomerates.     

Phase Equilibria and Structure of Solid Solutions in the La–Co–Fe–O System at 1100°C

Phase equilibria in the La–Co–Fe–O system are studied at 1100°C in air using samples prepared by the citrate, nitrate, and conventional ceramic routes. The stability regions and structures of solid solutions in the La–Co–Fe–O system are determined by x-ray powder diffraction: LaCo_{1 – y} Fe _y O_{3 –} (0 < y 0.25, sp. gr. R c; 0.775 y< 1, sp. gr. Pbnm), Co_{1 – y} Fe _y O (0 < y 0.13, NaCl-type structure, sp. gr. Fm3m), and Fe_{3 – x} Co _x O₄ (0.84 x 1.38, sp. gr. Fd3m). The structural parameters of phase-pure solid solutions are determined by the Rietveld method. The composition dependences of lattice parameters are presented for LaCo_{1 – y} Fe _y O_{3 –} (0 < y 0.25) and Fe_{3 – x} Co _x O₄ (0.84 x 1.38). The 1100°C isotherm of the pseudoternary system La₂O₃–CoO–Fe₂O₃ in air is constructed.