Phase relation studies in the CeO2–La2O3–Er2O3 system at 1500°C

Materials based on CeO₂–La₂O₃–Er₂O₃ system are promising candidates for a wide of applications, but the phase relationship has not been studied systematically previously. To address this challenge, the isothermal section of the phase diagram for 1500 °C was investigated. The phase relations in the CeO₂–La₂O₃–Er₂O₃ ternary system at 1500 °C were studied by X-ray diffraction and scanning electron microscopy in the overall concentration range. To study phase relationships at 1500 °C the as-repared samples were thermally treated in two stages: at 1100 °C (for 300 in air) and then at 1500 °C (for 70 h in air) in the furnaces with heating elements based on Fecral (H23U5T) and Superkanthal (MoSi2), respectively. The solid solutions based on various polymorphous forms of constituent phases and with perovskite-type structure of LaErO₃ (R) with orthorhombic distortions were revealed in the system. No new phases were found. The isothermal section of the phase diagram for the CeO₂–La₂O₃–Er₂O₃ system has been constructed. It was established that in the ternary CeO₂–La₂O₃–Er₂O₃ system there exist fields of solid solutions based on hexagonal (A) modification of La₂O₃, cubic modification of CeO₂ with fluorite-type structure (F), cubic modification Er₂O₃ and with perovskite-type structure of LaErO₃ (R) with orthorhombic distortions. The maximal solubility of ceria in LaErO₃ was found to be around ∼ 2 mol% CeO₂ along the section CeO₂–(50 mol % La₂O₃ –50 mol% Er₂O₃).     

Phase relation studies in the CeO2-Eu2O3 system at 1500 to 600 °C in air

Materials based on CeO₂-Eu₂O₃ system are promising candidates for a wide range of applications, but the phase relationship has not been studied systematically previously. To address this challenge, the subsection of the phase diagram for 600, 1100 and 1500 °C has been elucidated. Samples of different compositions have been prepared from nitrate acid solutions using conventional ceramic techniques; evaporation, drying, and calcinations. The phase relations in the binary CeO₂-Eu₂O₃ system at 600–1500 °C in air were studied from the heat treated samples using X-ray diffraction analysis, polarized light microscopy investigation and scanning electron microscopy in the overall concentration range. It was established that in the binary CeO₂-Eu₂O₃ system there exist fields of solid solutions based on monoclinic (B) modification of Eu₂O₃, cubic (C) modification of Eu₂O₃ and cubic modification of CeO₂ with fluorite-type structure (F). The systematic study that covered whole composition range excluded formation of new phases. The refined lattice parameters of the unit cells and the boundaries of the homogeneity fields for solid solutions were determined.     

Phase equilibrium in systems based on oxides of zirconium,lanthanum and samarium

According to the results of the samples studied by X-ray diffraction and microstructural analyzes the phase equilibria in the binary La₂O₃ – Sm₂O₃ and ternary ZrO₂ – La₂O₃ – Sm₂O₃ systems were studied. The boundaries of the phase fields of the binary system are specified and an isothermal cross section of the ternary state diagram of the ZrO₂ – La₂O₃ – Sm₂O₃ system at a temperature of 1500 °C is constructed. No new phases have been identified in the studied systems. It is established that in the ternary system ZrO₂ – La₂O₃ – Sm₂O₃ at 1500 °C fields of solid solutions on the basis of cubic (F) modification with structure of fluorite type, tetragonal (T) modification of ZrO₂, monoclinic (B) modifications of Sm₂O₃, hexagonal (A) are formed. La₂O₃, as well as an ordered phase with a structure of the type of pyrochlore Ln₂Zr₂O₇ (Py). The boundaries of the phase fields and the parameters of the unit cells of the formed phases are determined. A characteristic feature of this isothermal cross section is the formation of a continuous series of solid solutions based on the phase of the pyrochlore type La₂Zr₂O₇ (Sm₂Zr₂O₇). The limiting solubility of Sm₂O₃ in the ordered phase La₂Zr₂O₇ is 16 mol. % along the section Sm₂O₃- (67 mol.% ZrO₂ - 33 mol.% La₂O₃). The solubility of La₂O₃ in the solid solution Sm₂Zr₂O₇ is slightly less and is 11 mol. % along the section La₂O₃- (67 mol.% ZrO₂ - 33 mol.% Sm₂O₃). The isothermal cross-section of the state diagram of the ZrO₂ – La₂O₃ – Sm₂O₃ system at 1500 °C is characterized by the presence of three three-phase (Py + T + F), (A + Py + B), (Py + F + B) and eight two-phase (A + Py), (B + A), (B + Py), (F + B), (T + F), (Py + T), (F + Py-two) areas.     

Phase equilibria in the Bi2O3-CuO-Nb2O5 ternary system

A complete subsolidus ternary phase diagram of the Bi₂O₃-CuO-Nb₂O₅ (BCN) system was constructed. Careful firing control and phase analysis were applied to determine the phase assemblages and compatibilities over a wide range of temperatures, i.e. 700–925 °C. Phase-pure BCN pyrochlores were found to crystallise in cubic symmetry, space group Fd3m, No. 227 with lattice constants in the range of 10.4855 (5)<x<10.5321 (3). The mechanism of this limited subsolidus series could be represented by a general formula, Bi_3.08−xCu_1.84+2x/9Nb_3.08+7x/9O_14.16+6x/9 (0≤x≤0.36) wherein the reduction in Bi content was compensated by a proportion amount of copper and niobium together with non-stoichiometry in oxygen.     

Phase relation studies in the CeO2-La2O3 system at 1100-1500 °C

Materials based on CeO₂-La₂O₃ system are promising candidates for a wide range of applications, but the phase relationship has not been studied systematically previously. To address this challenge, the subsection of the phase diagram for 1100 and 1500 °C have been elucidated. Samples of different compositions have been prepared from nitrate acid solutions using conventional ceramic techniques; evaporation, drying, and calcinations. The phase relations in the binary CeO₂-La₂O₃ system at 1100-1500 °C were studied from the heat treated samples using X-ray diffraction analysis, petrographic investigation and scanning electron microscopy in the overall concentration range. It was established that in the binary CeO₂-La₂O₃ system there exist fields of solid solutions based on hexagonal (A) modification of La₂O₃, and cubic modification of CeO₂ with fluorite-type structure (F). The systematic study that covered whole composition range excluded formation of new phases. The refined lattice parameter of the unit cell and the boundaries of the homogeneity fields for solid solutions were determined.     

Integrated experimental phase equilibria study and thermodynamic modelling of the binary ZnO–Al2O3, ZnO–SiO2, Al2O3–SiO2 and ternary ZnO–Al2O3–SiO2 systems

Phase equilibria of the ZnO–SiO₂, Al₂O₃–SiO₂ and ZnO–Al₂O₃–SiO₂ systems at liquidus were characterized at 1340–1740 °C in air. The ZnO–Al₂O₃ subsolidus phase equilibria were derived from the experiments with the SiO₂- and CaO + SiO₂-containing slags. High-temperature equilibration on silica or platinum substrates, followed by quenching and direct measurement of Zn, Al, Si and Ca concentrations in the phases with the electron probe X-ray microanalysis (EPMA) was used to accurately characterize the system. Special attention was given to zincite phase that was shown to consist of two separate ranges of compositions: round-shaped low-Al zincite (<2 mol.% AlO_1.5) and platy high-Al zincite (4–11 mol.% AlO_1.5). A technique was developed for more accurate measurement of the ZnO solubility in the low-ZnO phases (corundum, mullite, tridymite and cristobalite) surrounded by the ZnO-containing slag, using l-line for Zn instead of K-line, avoiding the interference of secondary X-ray fluorescence. Solubility of ZnO was found to be below 0.03 mol.% in corundum and cristobalite, and below 0.3 mol.% in mullite. Present experimental data were used to obtain a self-consistent set of parameters of the thermodynamic models for all phases in this system using FactSage computer package. The modified quasichemical model with two sublattices (Zn²⁺, Al³⁺, Si⁴⁺) (O^2?) was used for the liquid slag phase; the compound energy formalism was used for the spinel (Zn²⁺,Al³⁺)[Zn²⁺,Al³⁺,Va]₂O^2-₄ and mullite Al³⁺₂(Al³⁺,Si⁴⁺) (O^2?,Va)₅ phases; the Bragg-Williams formalism was used for the zincite (ZnO, Al₂O₃); other solid phases (tridymite and cristobalite SiO₂, corundum Al₂O₃, and willemite Zn₂SiO₄) were described as stoichiometric. Present study is a part of the research program on the characterization of the multicomponent Pb–Zn–Cu–Fe–Ca–Si–O–S–Al–Mg–Cr–As–Sn–Sb–Bi–Ag–Au–Ni system.     

Experimental investigation of the phase relations in the SiO2-Dy2O3-CaO ternary system

This paper reports on the experimental investigation of the phase relations in the CaO-SiO₂-Dy₂O₃ system. CaO-SiO₂-Dy₂O₃ slags were equilibrated at 1773 and 1873 K for 86400 s in Ar and then quenched in water to determine the phase relations of the system. The composition of the equilibrated phases was measured by EPMA-WDS and XRD. The presence of ternary compounds and the solid solution and liquid regions were determined to construct the isothermal sections at 1773 and 1873 K of the ternary phase diagram. The data from this work will support further investigations on the feasibility to recover REEs through pyrometallurgical processing.     

Critical evaluation and thermodynamic optimization of the Na2O–FeO–Fe2O3–Al2O3–SiO2 system

A critical assessment and thermodynamic optimization of phase diagrams and thermodynamic properties of the entire Na₂O–FeO–Fe₂O₃–Al₂O₃–SiO₂ system were carried out at 1 atm total pressure. A set of optimized model parameters obtained for all phases present in this system reproduces available and reliable thermodynamic property and phase equilibrium data within experimental error limits from 298 K to above liquidus temperatures for all compositions and oxygen partial pressures from metallic Fe saturation to 1 atm. The Gibbs energy of liquid solution was described based on the Modified Quasichemical Model considering the possible formation of NaAlO₂ and NaFeO₂ associates in the liquid state. The solid solutions wüstite, spinel, feldspar, nepheline, carnegieite, mullite, corundum, clino-pyroxene, meta-oxides and Na-β″-alumina were treated within the framework of Compound Energy Formalism. The database of model parameters can be used to calculate any thermodynamic property and phase diagram section of the present system.     

Phase equilibria and microwave dielectric properties in the ternary La2O3–TiO2–Nb2O5 system

High-temperature phase relations in the La₂O₃–TiO₂–Nb₂O₅ ternary system were investigated at 1290 °C using SEM, EDS and XRD, and a subsolidus phase equilibrium diagram was constructed. It was demonstrated that the addition of the La_1/3NbO₃ to the La₂O₃:3TiO₂ mixture completely stabilizes a perovskite-La_2/3TiO₃ compound, which is otherwise not stable at stoichiometric composition. On the other hand, a mixture La₂O₃:TiO₂ =1:3 dissolves in La_1/3NbO₃ up to 15 mol% TiO₂. Moreover, a newly defined composition of compound La₃₀Ti₁₆Nb₄O₈₇ formed in the La₂O₃-rich part of the system and a solid solution La₃Ti₅Nb₁₀O_39.5–La₂Ti₂Nb₈O₂₇ were proposed. In the binary subsystem LaTiNbO₆-La_0.462Ti_0.386Nb_0.614O₃, the components exhibit opposite temperature dependence of resonant frequency in the microwave frequency range. Thus, the dielectric properties of the prepared ceramics can be tailored by varying the component concentration and thermally stable dielectric properties can be achieved for a composition with a LaTiNbO₆/La_0.462Ti_0.386Nb_0.614O₃ molar ratio of 0.27.     

Phase transformation and grain-boundary segregation in Al-Doped Li7La3Zr2O12 ceramics

Cubic phase garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al₂O₃. The reported ionic conductivities were variable due to the complicated Al³⁺-Li⁺ substitution and Li_xAlO_y segregation in Al-LLZO ceramics. This work prepared Li_7?3xAl_xLa₃Zr₂O₁₂ (x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution, and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li⁺ ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO₂ and LaAlO₃ segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li⁺ ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li_6.04Al_0.32La₃Zr₂O₁₂ ceramic delivers the optimum Li⁺ ion conductivity of 1.7 × 10^?4 S cm^?1 at 25 °C.     

Effect of La2O3 on Ru/CeO2-La2O3 Catalyst for Ammonia Synthesis

A series of CeO₂-La₂O₃ supported ruthenium catalysts were prepared by co-precipitation method and the as-obtained samples were characterized by N₂ physisorption, X-ray diffraction, CO chemisorption, H₂-TPR, H₂-TPD and XPS. The activity test shows that ammonia concentration of the catalyst with 10% La is 13.9% at 10 MPa, 10,000 h^?1, 450 °C, which is 17% higher than that of Ru/CeO₂. La doping can improve the activity of Ru-ceria catalyst for ammonia synthesis by facilitating the reduction of oxygen which subsists in the cerium oxide surface. In addition, it can be realized that the test of catalyst stability proves the stability performance of Ru/CeO₂-La₂O₃ catalyst within the reaction time of 55 h.     

Phase relations of CaO-Al2O3-Sc2O3 ternary system

We investigated the isothermal section of the CaO-Al₂O₃-Sc₂O₃ ternary system at 1773 and 1873 K for 24 hours in Ar, and quenched in water to determine the operative phase equilibrate. The composition of the phases in equilibrium was determined by electron probe microanalysis. The isothermal section phase diagram of two temperature points (1773 and 1873 K) is obtained. The 1773 K isothermal section consists of one liquid compound (L), six binary compounds (CaO+L, Ca₂Sc₆Al₆O₂₀+L C₃A+L, CaO.Sc₂O₃+L, CA+L, Ca₂Sc₆Al₆O₂₀+Sc₂O₃) and seven ternary compounds (Ca₂Sc₆Al₆O₂₀+Sc₂O₃+CA₆, Ca₂Sc₆Al₆O₂₀+Sc₂O₃+L, Ca₂Sc₆Al₆O₂₀+CA+L, Ca₂Sc₆Al₆O₂₀+CA₂+CA, Ca₂Sc₆Al₆O₂₀+CA₂+CA₆, CaO.Sc₂O₃+L+Sc₂O₃, C₃A+CaO+L). At 1873 K, we found one liquid compound (L), five binary compounds (CaO+L, Ca₂Sc₆Al₆O₂₀+L, CaO.Sc₂O₃+L, CA+L, Ca₂Sc₆Al₆O₂₀+Sc₂O₃₎ and six ternary compounds (Ca₂Sc₆Al₆O₂₀+Sc₂O₃+CA₆, Ca₂Sc₆Al₆O₂₀+Sc₂O₃+L, Ca₂Sc₆Al₆O₂₀+CA+L, Ca₂Sc₆Al₆O₂₀+CA₂+CA, Ca₂Sc₆Al₆O₂₀+CA₂+CA₆, CaO.Sc₂O₃+L+Sc₂O₃) to exist at the isothermal section. The experimental information obtained in the present work not only is essential for the thermodynamic assessment of the CaO-Al₂O₃-Sc₂O₃ ternary system, but also is important for further investigation on separation of rare earths from metallurgical slags and rare-earth recovery.     

Ion exchange equilibria in binary and ternary systems

Simple mathematical models for binary and ternary ion exchange equilibria were developed to predict selectivity coefficients and resin capacities from a simple experiment to within acceptable engineering accuracy limits. Batch equilibrium experimental investigations were undertaken to test the models for binary systems (Ni-Na, Cu-Na, Zn-Na, Cd-Na and Pb-Na) and ternary systems (Ni-Cu-Na, Cd-Ni-Na, Cd-Cu-Na and Pb-Cu-Na) with a commercial DOWEX HCR-W2 resin. Binary parameters were used to predict ternary equilibria. It was found that good agreement between the predicted and experimental values was obtained when the binary selectivity coefficients of the two competing heavy metal ions in the ternary system were either almost equal or differed by a factor as large as five.     

H_2和CO_2在甲苯中的二元系相平衡特性研究

建立了1套连续式热力学平衡测量装置,在压力1．5～10 MPa,温度303～343 K范围内,测量了H_2和CO_2在甲苯中的二元系平衡溶解度数据。结果表明,2种气体在甲苯中的溶解度均随压力增大而增加。H_2在甲苯中的溶解度随温度升高而增大。CO_2在甲苯中的溶解度则随温度升高而减小。考虑1个二元相互作用参数,将实验数据用Peng-Robinson状态方程式进行关联,可以获得满意的计算精度。     

MgO-TiO_2-La_2O_3系氧化铝陶瓷的力学性能及物相分析

采用MgO-TiO2-La2O3为烧结助剂,利用低温烧结技术制备95氧化铝瓷。研究了烧成温度和助剂含量对氧化铝陶瓷力学性能及物相组成的影响。结果表明:在MgO含量为1.5wt%,TiO2为1.0wt%,La2O3为2.5wt%,1500℃保温2h可得到抗弯强度和硬度分别为348.94MPa和79.6HRA的氧化铝陶瓷。     

Origin of extrinsic dielectric loss in 1:2 ordered,single-phase BaMg1/3Ta2/3O3

Among the family of temperature-compensated microwave dielectric ceramics, BaMg_1/3Ta_2/3O₃ shows the lowest dielectric loss and remains a material of choice for state-of-the-art airborne and land-based communication systems. We report on the compositional stability range, microwave dielectric properties, and the degree of atomic order of the title compound within the BaO–MgO–Ta₂O₅ ternary diagram. In most cases an atomic order is robust to the deviation from stoichiometry with an exception of Ba-rich and/or Ta-deficient samples which favor (partial) disorder. We further demonstrate that the dense, atomically ordered BaMg_1/3Ta_2/3O₃ ceramic shows large variation of dielectric loss within a single phase composition region – a clear message that the dielectric loss in practical ceramics is dominated by extrinsic sources and that the cation order alone is insufficient to achieve a minimum dielectric loss in BaMg_1/3Ta_2/3O₃. The low-temperature dielectric relaxation studies suggest that the extrinsic dielectric loss in the title compound is due to the ‘rattling’ of the off-centered Mg²⁺ ions misplaced at the Ba sites. Controlled deviation from the BaMg_1/3Ta_2/3O₃ stoichiometry toward the Mg-deficient region leads to suppression of the extrinsic dielectric loss as a result of the reduced chemical activity of Mg ion.     

Thermal and magnetic properties of new scheelite type Cd1−3x□xGd2xMoO4 ceramic materials

The limited scheelite type Cd_1−3x□_xGd_2xMoO₄ solid solution, where 0 < x ≤ 0.25 and □ are cationic vacancies have been successfully synthesized by high-temperature annealing of CdMoO₄/Gd₂(MoO₄)₃ mixtures composed of 50.00 mol.% and less of Gd₂(MoO₄)₃. The obtained materials as well as CdMoO₄ and Gd₂(MoO₄)₃ were characterized by powder XRD, DTA–TG, DSC, and SEM techniques. A phase diagram of the pseudobinary CdMoO₄–Gd₂(MoO₄)₃ system was constructed. The eutectic point corresponds to 1350 ± 5 K and ∼70.00 mol.% of Gd₂(MoO₄)₃ in an initial CdMoO₄/Gd₂(MoO₄)₃ mixture. With decreasing of Gd³⁺ amount in the crystal lattice of CdMoO₄, a melting point of the Cd_1−3x□_xGd_2xMoO₄ solid solution increases from 1351 (x = 0.25) to 1408 K (x = 0). EPR method was used to identify the paramagnetic Gd³⁺centers in Cd_1−3x□_xGd_2xMoO₄ for different values of x parameter as well as to select biphasic samples containing both Cd_0.2500□_0.2500Gd_0.5000MoO₄ and Gd₂(MoO₄)₃.     

Measurement and correlation of solid–liquid phase equilibria for binary and ternary systems consisting of N-vinylpyrrolidone, 2-pyrrolidone and water

The solid–liquid equilibria(SLE)for binary and ternary systems consisting of N-Vinylpyrrolidone(NVP),2-Pyrrolidone(2-P)and water are measured.The phase diagrams of NVP(1)+2-P(2),NVP(1)+water(2),NVP(1)+2-P(2)+1 wt%water(3)and NVP(1)+2-P(2)+2 wt%water(3)are identified as simple eutectic type with the eutectic points at 263.75 K(x_(1E)=0.5427),251.65 K(x_(1E)=0.3722),260.25 K(x_(1E)=0.5031)and256.55 K(x_(1E)=0.4684),respectively.The phase diagram of 2-P(1)+water(2)has two eutectic points(x_(1E)=0.1236,T_E=259.15 K and x_(1E)=0.7831,T_E=286.15 K)and one congruent melting point(x_(1C)=0.4997,T_C=303.55 K)because of the generation of a congruently melting addition compound:2-P·H_2O.The ideal solubility and the UNIFAC models were applied to predict the SLE,while the Wilson and NRTL models were employed in correlating the experimental data.The best correlation of the SLE data has been obtained by the Wilson model for the binary system of NVP+2-P.The UNIFAC model gives more satisfactory predictions than the ideal solubility model.     

High-density nanoprecipitation mechanism and microstructure evolution of high-performance Al2O3/ZrO2 nanocomposite ceramics

Al₂O₃/ZrO₂ supersaturated solid solution micro-powders (AZ-SSP) with three components were successfully obtained by combustion synthesis assisted rapid water cooling, and their nanoprecipitation mechanism and microstructure evolution were studied by phase field simulation and hot-press sintering. The results show that AZ-SSP could be used to fabricate Al₂O₃/ZrO₂ nanocomposite ceramics (AZNC) with intragranular-intercrystalline microstructures by high-density nanoprecipitation, consistent with microstructures of heat-treated AZ-SSP via the phase field simulation. There were three simulated nanostructures of spherical and elongated particles in A57Z-SSP or A15Z-SSP and interlocking structures in A36Z-SSP. The submicro-crystals of A57ZNC and A15ZNC contain high-density nano- and supra-nano-particles, and the fracture toughness of these two ceramics can reach up to 10.37 ± 0.37 MPa·m^1/2 and 12.63 ± 0.36 MPa·m^1/2, respectively. Hence, the preparation method of ultra-fine structures by supersaturated solid solution has far-reaching guiding significance for various nanoceramics.     

The quasi ternary system TiB2-CrB2-WB2 between 1500 and 1900°C and the related quasi binary subsystems

The quasi-ternary TiB₂-CrB₂-WB₂ and the related quasi-binary subsystems were investigated by means of hot pressing and pressureless dilatometry in the temperature range between 1650 and 1900 °C. Long-term annealing up to 14 h was necessary for equilibration. Thus, samples were obtained first by densification and then by subsequent cooling to the respective temperature with continuous annealing for up to 16 h in some cases.In all binary subsystems the low-temperature range of the solidus and the liquidus lines could be determined. The CrB₂-WB₂ and the TiB₂-WB₂ systems are of eutectic type while the CrB₂-TiB₂ shows a continuous solid solubility.Furthermore, the miscibility gap proposed earlier for the CrB₂-TiB₂ could not be proven. The borders of the large homogeneity range of the AlB₂-type (Ti,W,Cr)B₂ solid solution were described. The presence of less than 5 mol% of CrB₂ aids accommodating W into the AlB₂-structure which agrees with previous sintering studies very well. Within the ternary composition range no indication for a ternary eutectic was found up to 1900 °C. Implications of impurities to the obtained phase diagrams are discussed.