Phase Relations in the Systems SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K

Phase relations in the systems SrO-Y₂O₃-CuO-O₂ and CaO-Y₂O₃-CuO-O₂ at 1173 K were estab-lished by equilibrating different compositions in flowing oxygen gas at a pressure of 1.01 × 10⁵ Pa. The quenched samples were examined by optical microscopy, X-ray diffraction (XRD), energy dis-persive analysis of X-rays (EDAX), and electron spin resonance (ESR). In the system SrO-Y₂O₃-CuO-O₂, except for the limited substitution of Y₃+ for Sr₂+ ions in the ternary oxide Sr₁₄ Cu₂₄O₄₁, no new quaternary phase was found to be stable. The compositions corresponding to the solid solution Sr_14-xY_xCu₂₄O₄₁ and the compound SrCuO₂+δ lie above the plane containing SrO, Y₂O₃, and CuO, displaced towards the oxygen apex. However, in the system CaO-Y₂O₃-CuO-O₂ at 1173 K, all the condensed phases lie on the plane containing CaO, Y₂O₃, and CuO, and a new quaternary oxide YCa₂Cu₃O_6.5 is present. The quaternary phase has a composition that lies at the center of the non-stoichiometric field of the analogous phase YBa₂Cu₃O_7-δ in the BaO-Y₂O₃-CuO-O₂ system. The com-pound YCa₂Cu₃O_6.5 has the tetragonal structure and does not become superconducting at low temperature. Surprisingly, phase relations in the three systems CaO-Y₂O₃-CuO-O₂, SrO-Y₂O₃-CuO-O₂, and BaO-Y₂O₃-CuO-O₂ are found to be quite different.     

The CaO-SrO-CuO-O2 system: Phase equilibria and thermodynamic properties at 1123 K

Phase relationships in the CaO-SrO-CuO system in pure oxygen at 1.01 × 10⁵ Pa pressure were determined by equilibrating different compositions at 1123 K for ∼120 h and analyzing the phases present in the quenched samples using X-ray diffraction (XRD), optical and scanning electron microscopy, and energy dispersive analysis of X-rays (EDAX). Four solid solution series were observed in the system. The Ca_wSr_1-wO monoxide solid solution with rock-salt structure was found to exhibit an asymmetric miscibility gap. The mixing properties of the monoxide system were deduced using a subregular solution model. For the (Ca_xSr_1-x)₂CuO₃ series, a complete solid solution range with orthorhombic space groupImmm was obtained. Calcium substituted for strontium up to 68 at.% in SrCuO_2+δ and 51.5 at.% in Sr₁₄Cu₂₄O_41-δ. The tie lines between the solid solutions were determined accurately. The activity-composition relations in (Ca_xSr_1-x)₂CuO₃, Ca_ySr_1-y,CuO_2+δ, and (Ca_zSr_1-z)₁₄Cu₂₄O_41-δ solid solutions were determined from experimental tie lines. Activities in the (Ca_xSr_1-x)₂CuO₃ and Ca_ySr_1-yCuO_2+δ series were close to the predictions of the Temkin model. The behavior of the (Ca_zSr_1-z)₁₄Cu₂₄O_41-δ solid solution was more complex, with the activity of SrCu_(24/14)O_(41-δ)/14 exhibiting both positive and negative deviations from ideality. Gibbs energy of formation of the CaCuO_2+δ metastable phase at 1123 K was deduced from an analysis of the phase diagram.     

Phase Relations in the System CaO-Fe2O3-Y2O3 at 1273?K and Compatibility Between Y1?xCaxFeO3?0.5x and Stabilized Zirconia

Phase relations in the system CaO-Fe₂O₃-Y₂O₃ in air (( P_\textO2 P_{{{\text{O}}_{2} }} /P°) = 0.21) were explored by equilibrating samples representing eleven compositions in the ternary at 1273 K, followed by quenching to room temperature and phase identification using XRD. Limited mutual solubility was observed between YFeO₃ and Ca₂Fe₂O₅. No quaternary oxide was identified. An isothermal section of the phase diagram at 1273 K was constructed from the results. Five three-phase regions and four extended two-phase regions were observed. The extended two-phase regions arise from the limited solid solutions based on the ternary oxides YFeO₃ and Ca₂Fe₂O₅. Activities of CaO, Fe₂O₃ and Y₂O₃ in the three-phase fields were computed using recently measured thermodynamic data on the ternary oxides. The experimental phase diagram is consistent with thermodynamic data. The computed activities of CaO indicate that compositions of CaO-doped YFeO₃ exhibiting good electrical conductivity are not compatible with zirconia-based electrolytes; CaO will react with ZrO₂ to form CaZrO₃.     

Enhancement of upconversion luminescence of Y2O3:Er nanocrystals by codoping Li-Zn

The upconversion (UC) luminescence in sol-gel synthesized Li⁺, Zn²⁺, or Li⁺-Zn²⁺ codoped Y₂O₃:Er³⁺ nanocrystals were investigated under the excitation of a 970 nm diode laser. Compared to undoped Y₂O₃:Er³⁺ samples, proper doping of Li⁺-Zn²⁺ leads to an drastic increase of the UC luminescence centered at 560 nm by a factor of 28. The UC luminescence enhancement is a result of the increased lifetime of the intermediate state ⁴I_11/2 (Er). The intensity ratio of the green over red emissions (green/red) is also affected by the codoping of Zn²⁺, Li⁺ and Li⁺-Zn²⁺ ions. Our results demonstrated that the Li⁺-Zn²⁺ codoping in Y₂O₃:Er³⁺ phosphors produced remarkable enhancement of the UC luminescence and green/red ratio, making this nanocrystal a promising candidate for photonic and biological applications.     

Effect of CuO on the sintering temperature and piezoelectric properties of MnO2-doped 0.75Pb(Zr0.47Ti0.53)O3-0.25Pb(Zn1/3Nb2/3)O3 ceramics

The sintering temperature of 0.75Pb(Zr_0.47Ti_0.53)O₃-0.25Pb(Zn_1/3Nb_2/3)O₃ ceramics containing 1.5 mol% MnO₂ was decreased from 930 to 850 °C with the addition of CuO. The CuO reacted with the PbO and formed a liquid phase during the sintering, which assisted the densification of the specimens. Most of the Cu²⁺ ions existed in the CuO second phase, thereby preventing any possible hardening effect from the Cu²⁺ ions. Variations of the k_p, Q_m, ?₃^T/?₀ and d₃₃ values with CuO were similar to that of the relative density. The specimen containing 0.5 mol% CuO sintered at 850 °C showed the good piezoelectric properties of k_p = 0.5, Q_m = 1000, ?₃^T/?₀ = 1750 and d₃₃ = 300 pC/N.     

Complex impedance analysis of (Y2O3 + CeO2)-YCr0.5Mn0.5O3 composite NTC ceramics

Ceramic compositions based on (aY₂O₃ + bCeO₂)-0.4YCr_0.5Mn_0.5O₃ (a + b = 0.6) were prepared by conventional solid state reaction at 1200 °C, and sintered under air atmosphere at 1600 °C. For 0 ≤ a < 0.6, XRD patterns have shown that the major phases presented in the calcined powders are Y₂O₃, CeO₂ and orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase, respectively. SEM and EDAX observations confirm the YCr_0.5Mn_0.5O₃ phases mostly exist at the grain, whereas the Y₂O₃ and CeO₂ phases mainly exist at the grain boundaries. Complex impedance analysis shows that, for 0 < a ≤ 0.6, single semicircular arc whose shape does not show any change with temperature. Nevertheless, for a = 0, two overlapping semicircular arcs are observed at and above 300 °C. The grain boundary properties exhibit thermistor parameters with a negative temperature coefficient characteristic. The relaxation behavior and conduction for the grain boundary could be due to a space-charge relaxation mechanism and oxygen vacancies, respectively.     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Y2O3/Sn-58Bi复合钎料制备及其性能分析

文中通过粉末冶金法制备了Y₂O₃/Sn-58Bi复合钎料.结果表明,添加少量Y₂O₃,对复合钎料熔点影响较小;随着Y₂O₃质量分数提高,复合钎料的密度和显微维氏硬度先升高后降低;复合钎料的润湿角表现出相反的趋势,随着Y₂O₃质量分数提高,复合钎料的润湿角先降低后升高.通过测试Sn-58Bi钎料和0.1%（质量分数）Y₂O₃/Sn-58Bi复合钎料拉伸试样的力学性能发现,添加质量分数为0.1%的Y₂O₃对复合钎料强度稍有提高,但能明显提高复合钎料的延展性,从而解决传统Sn-58Bi钎料较脆的难题.通过观察钎料拉伸断口发现,添加Y₂O₃能够细化复合钎料微观组织,使裂纹沿着断裂方向扩展时受到阻碍,抑制了钎料脆性断裂的趋势.     

Thermodynamic optimization of the Na2O-B2O3 pseudo-binary system

The Na₂O-B₂O₃ system is thermodynamically optimized by means of the CALPHAD method. A two-sublattice ionic solution model, (Na⁺¹)_P(O⁻²,BO₃ ⁻³,B₄O₇ ⁻²,B₃O_4.5)_Q, has been used to describe the liquid phase. All the solid phases were treated as stoichiometric compounds. A set of thermodynamic parameters, which can reproduce most experimental data of both phase diagram and thermodynamic properties, was obtained. Comparisons between the calculated results and experimental data are presented.     

Critical thermodynamic evaluation and optimization of the MgO-Al2O3, CaO-MgO-Al2O3, and MgO-Al2O3-SiO2 Systems

A complete literature review, critical evaluation, and thermodynamic modeling of the phase diagrams and thermodynamic properties of all oxide phases in the MgO-Al₂O₃, CaO-MgO-Al₂O₃, and MgO-Al₂O₃-SiO₂ systems at 1 bar total pressure are presented. Optimized model equations for the thermodynamic properties of all phases are obtained that reproduce all available thermodynamic and phase equilibrium data within experimental error limits from 25 °C to above the liquidus temperatures at all compositions. The database of the model parameters can be used along with software for Gibbs energy minimization to calculate all thermodynamic properties and any type of phase diagram section. The modified quasichemical model was used for the liquid slag phase and sublattice models, based upon the compound energy formalism, were used for the spinel, pyroxene, and monoxide solid solutions. The use of physically reasonable models means that the models can be used to predict thermodynamic properties and phase equilibria in composition and temperature regions where data are not available.     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

纳米级和微米级稀土氧化物掺杂W-La2O3-Y2O3-ZrO2 阴极尖端的组织和性能

使用粉末冶金法将纳米级(70–80 nm)和微米级(500–600 nm)稀土氧化物(La₂O₃,Y₂O₃)与钨粉混合,随后通过冷等静压、中频感应烧结、旋锻、拉拔等一系列工艺制备了W-1.5La₂O₃-0.1Y₂O₃-0.1ZrO₂(质量分数,%)材料。对含有纳米和微米尺寸稀土氧化物的阴极样品使用相同的焊接电流,分别进行了0.5、1、2 h的氩弧焊。结果表明,具有纳米级稀土氧化物的样品在焊接过程中表现出更高的工作稳定性,烧损同比降低了近85.4%。此外,随着工作时间的延长,阴极尖端不同区域的稀土氧化物聚集度显著增加。结合COMSOL Multiphysics温度模拟发现,第二相的扩散活化能降低了近34%。这是因为更为细小的第二相有效地控制了钨基体组织的演变,保留了大量晶界作为通道,促进了活性物质在电子发射过程中的扩散。     

Subsolidus phase relations of the SrO–Ta2O5–CuO system at 900 °C in air

The subsolidus phase relations of the SrO–Ta₂O₅–CuO system were investigated in air. The samples were equilibrated at 900 °C. The ternary oxide Sr₃Ta₂CuO₉ compound is stable under these conditions. This phase presents a solid solution range, its actual composition being Sr₃Ta_2−xCu_1+xO_9+δ with 0.0 ≤ x ≤ 0.2. Up to about 5 at.% Cu can be incorporated in the Sr_3−xTa_1+xO_5.5+δ phase. Similarities with the SrO–Nb₂O₅–CuO system are discussed.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

Role of Al2O3 layer in oxidation resistance of Cu-Al dilute alloys pre-annealed in H2 atmospheres

Copper was alloyed with small amounts of Al (0.2, 0.5, 1.0 and 2.0 mass%) to improve the oxidation resistance. Copper (6 N) and the Cu-Al alloys were oxidized at 773-1173 K in 0.1 MPa oxygen atmosphere after hydrogen annealing at 873 K. Continuous very thin Al₂O₃ layers were formed on the surface of all Cu-Al dilute alloys during the hydrogen annealing. Oxidation resistance of Cu-Al alloys was improved especially for Cu-2.0Al at 773-973 K, while it decreases on increasing the oxidation temperature. Cu-Al alloys followed the parabolic rate law at 1173 K, but most of other cases do not at and below 1073 K. Oxidation resistance for Cu-Al alloys was found relevant to the maintenance of the thin Al₂O₃ layer at the Cu₂O/Cu-Al alloy interface.     

Synthesis and superconductivity of Y2Ba1Cu1O5 and Pt added Nd1Ba2Cu3O7?y bulk superconductor

Nd₁Ba₂Cu₃O_7−y (Ndl23) bulk superconductor with T_c>77K was prepared by a melt process under 1 atm pure oxygen and reduced oxygen partial pressures. The addition of Y₂Ba₁Cu₁O₅ (Y211) particles suppressed the generation of microcracks during oxygenation in resulting in the dispersion of Y211 fine particles. The addition of a small amount of Pt resulted in the reduction of the size of Y211 particles. The oxygen partial pressure (Po₂) of 0.01 atm was the optimum atmosphere for the synthesis of Ndl23 in which Y211 particles were dispersed finely and homogeneously. The addition of Y211 and Pt enhanced the flux pinning force in a melt-processed Ndl23 specimen because the presence of Y atoms in a melt phase suppressed, to some extent, the substitution of Nd on Ba site in an Ndl23 crystal prepared by a melt process.     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3, CrO-Cr2O3-Al2O3, and CrO-Cr2O3-CaO systems

Available thermodynamic and phase diagram data have been critically assessed for all phases in the CrO-Cr₂O₃, CrO-Cr₂O₂-Al₂O₃, and CrO-Cr₂O₂-CaO systems from 298 K to above the liquidus temperatures and for oxygen partial pressures ranging from equilibrium with metallic Cr to equilibrium with air in the case of the first two systems and toP _{O 2} = 10⁻³ atm for the CrO-Cr₂O₃-CaO system. All reliable data have been simultaneously optimized to obtain one set of model equations for the Gibbs energy of the liquid slag and all solid phases as functions of composition and temperature. The modified quasichemical model was used for the slag. The models permit phase equilibria to be calculated for regions of composition, temperature, and oxygen potential where data are not available.     

Effect of Ca-doping on the structural and electrical properties of CuY1−xCaxO2 (0 ≤x ≤0.10) ceramics

Delafossites CuY_1−xCa_xO₂ (0 ≤x ≤0.10) ceramics have been prepared by solid state reaction using Cu₂O, Y₂O₃ and CaCO₃. Liquid phase sintering, which obviously accelerates the reaction speed of Cu₂O-Y₂O₃-CaCO₃ system and promotes the formation of CuYO₂ phase is evidenced for the Ca-doped samples. During the sintering process, CuO can react with CaO to form two intermediate compounds, CaCu₂O₃ and Ca₂CuO₃, which decompose into CaO and liquid phase during 1273-1323 K. In the dopant range of 0 ≤x ≤0.10, both electrical conductivity and density of the samples are increased by Ca-doping. The room temperature conductivity of CuY_0.94Ca_0.06O₂ is more than four orders of magnitude higher than that of CuYO₂.     

Enthalpy of formation of selected mixed oxides in a CaO-SrO-Bi2O3-Nb2O5 system

The heats of drop-solution in 3Na₂O + 4MoO₃ melt at 973 K and 1073 K for calcium and strontium carbonates, Bi₂O₃, Nb₂O₅ and several stoichiometric mixed oxides in CaO-Nb₂O₅, SrO-Nb₂O₅ and Bi₂O₃-Nb₂O₅ systems were measured using a Setaram Multi HTC-96 calorimeter. The values of enthalpy of formation from constituent binary oxides at 298 K, Δ_oxH, were derived for the mixed oxides under investigation: Δ_oxH(CaNb₂O₆) = −132.0 ± 23.8 kJ mol⁻¹, Δ_oxH(Ca₂Nb₂O₇) = −208.0 ± 31.9 kJ mol⁻¹, Δ_oxH(SrNb₂O₆) = −167.9 ± 19.1 kJ mol⁻¹, Δ_oxH(Sr₂Nb₂O₇) = −289.2 ± 37.5 kJ mol⁻¹ and Δ_oxH(BiNbO₄) = −41.9 ± 11.1 kJ mol⁻¹. Additionally, the values Δ_oxH for other mixed oxides with different stoichiometries were estimated on the basis of these experimental results.