Influence of structure and temperature on the thermal conductivity of molten CaO–B2O3

The effect of the temperature and borate structure on the thermal conductivity of the molten CaO–B₂O₃ binary system was investigated. The thermal conductivity was measured from 1573 K to approximately the liquidus temperature using a transient hot‐wire method, and was found to decrease with increasing temperature. The temperature dependence of the thermal conductivity in the molten oxide system was interpreted in terms of the lifetime of phonon‐like excitations and Maxwell relaxation times. The short‐range order borate structure was investigated through magic angle spinning (MAS) and triple‐quantum MAS (3Q‐MAS) NMR. Although the content of 4‐coordinated boron was not significantly affected by the addition of CaO, structural changes associated with the fraction of 3‐coordinated boron in ring and non‐ring sites were observed. The Raman spectra showed that the intermediate range order borate structure was changed from boroxyl rings to chain‐type metaborate units at higher CaO concentrations. The thermal conductivity decreased with decreasing BO_1.5/CaO ratio, owing to the depolymerization of the borate network.     

Subsolidus Phase Relationship in the CaO–CuO–TiO2 Ternary System at 950°C in Air

The subsolidus phase relationship in the CaO–CuO–TiO₂ ternary system at 950°C in air was investigated. Total 26 samples having various nominal compositions were prepared by the solid‐state reaction at 950°C in air, and their equilibrium phases were analyzed by powder X‐ray diffraction (XRD). The CaCu₃Ti₄O₁₂ phase exhibits variable stoichiometry and forms as the Ca_1?xCu_3+xTi₄O₁₂‐type (?0.019 ≤x ≤0.048) solid solution at 950°C in air. On the basis of our results and previous reports on the binary phase diagrams, the subsolidus phase diagram of the CaO–CuO–TiO₂ ternary system could be constructed at 950°C in air.     

Reaction Pathway of Combustion Synthesis of Ti5Si3 in Cu–Ti–Si System

The reaction pathway of combustion synthesis (CS) of Ti₅Si₃ in Cu–Ti–Si system was explored through a delicate microstructure and phase analysis on the resultant products during differential thermal analysis (DTA). The formation of Cu–Si eutectic liquids plays a key role in the reaction pathway, which provides easy route for reactant transfer and accelerates the occurrence of complete reaction. Cu initially reacted with Si to form Cu₃Si by a solid‐state diffusion reaction, which further reacted with Cu to form Cu–Si liquids at the eutectic point of ~802°C; then Ti was dissolved into the surrounding Cu–Si liquids and led to the formation of Cu–Ti–Si ternary liquids; finally, Ti₅Si₃ was precipitated out of the saturated liquids by a solution–reaction–precipitation mechanism. The reaction pathway in CS of titanium silicide (Ti₅Si₃) could be described briefly as: Cu_(s) + Ti_(s) + Si_(s)→Cu₃Si_(s) + Ti_(s) + Si_(s)→(Cu–Si)_(l) + Ti_(s)→(Cu–Ti–Si)_(l)→Cu_(l) + Ti₅Si_3(s).     

A Cu–Pd–V System Filler Alloy for Silicon Nitride Ceramic Joining and the Interfacial Reactions

A Cu–Pd–V brazing alloy with the composition of Cu–(38.0~42.0)Pd–(7.0~10.0)V (in wt.%) was designed as a filler for joining Si₃N₄. Its wettability on Si₃N₄ ceramic was measured with the sessile drop method. It was shown that the Cu–Pd–V alloy gave a contact angle of 71° at 1473 K. The filler alloy was fabricated into foils with a thickness of 0.15 mm. The Si₃N₄–Si₃N₄ joints brazed at 1443 K for 10 min exhibit average three‐point bend strength of 263 MPa at room temperature, and the joint strengths at 973 K and 1073 K are 277 MPa and 218 MPa, respectively. The analysis results of SEM, XRD, and TEM for the brazed joint indicate the presence of V₂N at the surface of the Si₃N₄. The increase of the thickness of V₂N reaction layer obeyed parabolic law, and the parabolic rate constant (k) can be described as k = 2.8739 × 10^?9 exp(?162989.4/RT) m²/s. Pd₂Si and Cu₃Pd compounds as well as (Cu, Pd) solid solution were detected in the central part of the joints. The presence of (Cu, Pd) phases and especially refractory Pd₂Si compounds within the joints should contribute to the stable high‐temperature property. The interfacial reaction mechanisms were discussed.     

Selected Phase Equilibria Studies in the Al2O3–CaO–SiO2 System

The Al₂O₃–CaO–SiO₂ system provides the basis for describing many important chemical processes. Although the system has previously been extensively studied, recent advances in experimental technique have provided the opportunity to obtain accurate liquidus measurements in the low‐silica region at fixed temperatures. The experimental procedures involve equilibration of high‐purity oxide powder mixtures at selected temperatures, rapid quenching, and accurate measurement of phase compositions using electron probe X‐ray microanalysis. The liquidus isotherms have been determined at selected temperatures between 1503 and 1873 K in the anorthite, gehlenite, pseudowollastonite, corundum, CaAl₁₂O₁₉, CaAl₂O₆, lime, Ca₃SiO₃, and Ca₂SiO₄ primary phase fields. The results are compared with currently available thermodynamic model predictions of the phase chemistry.     

A Novel Top‐Seeded Infiltration Growth Technique for Fabricating Y–Ba–Cu–O Single‐Grain Superconductor Nano‐Composites

Top‐seed infiltration and growth technique (TSIG) is proposed to fabricate Y–Ba–Cu–O (YBCO) single‐grain superconductor nano‐composites, in which a solid source composition of nano‐Y₂O₃ + BaCuO₂ and a liquid source composition of Y₂O₃ + 10BaO + 16CuO are employed. As can be seen, this novel technique uses just one source of precursor powder of BaCuO₂, so it is more simplified and efficient. Microstructural observation indicates that fine Y₂BaCuO₅ (Y‐211) inclusions with a size from dozens of nanometers to about one hundred nanometers are successfully introduced in YBa₂Cu₃O_7?x (Y‐123) superconducting matrix, which can act as more effective pinning centers for improving the bulk performance. Superconducting property measurement shows that, a maximum trapped field of 0.36044 T is present at the center of the sample after magnetization by a permanent magnet (B = 0.5 T). These results prove that our proposed TSIG technique is a practical method for fabricating YBCO bulk superconductor nano‐composites with high performance.     

Thermodynamic Assessment of the Pr–O System

The Calphad method was used to perform a thermodynamic assessment of the Pr–O system. Compound energy formalism representations were developed for the fluorite α‐PrO_2–x and bixbyite σ‐Pr₃O_{5 ± x} solid solutions while the two‐sublattice liquid model was used to describe the binary melt. The series of phases between Pr₂O₃ and PrO₂ were taken to be stoichiometric. Equilibrium oxygen pressure, phase equilibria, and enthalpy data were used to optimize the adjustable parameters of the models for a self‐consistent representation of the thermodynamic behavior of the Pr–O system from 298 K to melting.     

Preparation of waste-based Cu–Cu2O/SiO2 photocatalyst from serpentine tailings and waste printed circuit boards and photoreduction of Cr(VI)

In China, a large amount of serpentine tailings and waste printed circuit boards (WPCBs) are produced every year. Serpentine tailings contain about 43% SiO₂ and WPCBs contain about 20% Cu. Reusing their resources can not only solve the problem of environmental pollution, but also produce certain economic benefits. In this study, waste-based SiO₂ support, waste-based Cu–Cu₂O and Cu–Cu₂O/SiO₂ photocatalyst were prepared using serpentine tailings and WPCBs as Si and Cu sources. The waste-based SiO₂ of 750 nm particle size was obtained by precipitation of 0.7 mol/L Na₂SiO₃ solution from the serpentine tailings and its specific surface area reached 57.72 m²/g after 600 °C calcination. Cu and the waste-based Cu–Cu₂O were loaded on the waste-based Cu₂O and SiO₂ support, respectively, and the phase structure of the catalysts has not changed by the characterization of SEM, XRD and XPS. The activity of the photocatalytic reduction of Cr (VI) with the waste-based catalysts showed in the following order: Cu₂O < Cu₂O/SiO₂<Cu–Cu₂O < Cu–Cu₂O/SiO₂, inferring by the investigation of photoelectric properties that Cu prevented the recombination of Cu₂O electron-hole pairs, the Cu–Cu₂O dispersed on SiO₂ support surface to obtain a higher specific surface area. The waste-based Cu–Cu₂O/SiO₂ photocatalyst showed no obvious deactivation after 5 cycles. The mechanism revealed that photogenerated electrons are the major reactive species for the photodegradation of Cr (VI). The study indicates that the waste-based Cu–Cu₂O/SiO₂ is potentially a developed, low-cost catalyst from sustainable resources. The production of Cu–Cu₂O/SiO₂ photocatalyst by using WPCBs and serpentine tailings represents the potential usage of waste into valuable material.     

Combined experimental and computational investigation of thermodynamics and phase equilibria in the CaO–TiO2 system

Phase relations in the CaO–TiO₂ system are of considerable interest in geology, metallurgy, and ceramics. Despite a number of studies of phase equilibria in the CaO–TiO₂ system, there are still some open questions regarding the stability of intermediate compounds. In this work, a series of specimens with different CaO:TiO₂ ratios were prepared by solid‐state reaction. The heat capacities of Ca₃Ti₂O₇ and Ca₄Ti₃O₁₀ from 300 to 1073 K were measured by differential scanning calorimetry and their formation enthalpies from the component oxides at 298 K were measured by high temperature oxide melt solution calorimetry. Using phase diagram information and thermodynamic data from the literature and the present measurements, thermodynamic optimization of the CaO–TiO₂ system was carried out by the CALPHAD technique. The phase diagram and the thermodynamic properties of the CaO–TiO₂ system were calculated using the obtained thermodynamic database, which clarify the stable and metastable phase equilibria of the system. The thermodynamic stability of the various compounds was discussed.     

Selective steam reforming of methanol over silica-supported copper catalyst prepared by sol–gel method

Silica-supported copper prepared by a sol–gel method can selectively catalyze methanol steam reforming to hydrogen and carbon dioxide at 250 °C. The catalytic activity increases with the copper content up to 40 wt.%. The selectivity to carbon monoxide with the catalysts containing 20–40 wt.% of copper is significantly lower than that with a commercial Cu/ZnO/Al₂O₃ catalyst. Copper particles are highly dispersed in the catalyst whose Cu content is 20 wt.% or less. After the reaction at 250 °C the particles are present as Cu₂O with the mean crystallite size less than 4 nm. In the catalyst with the Cu content of 30–50 wt.%, the fine Cu₂O particles coexist with large metallic Cu particles whose mean crystallite size is 30–40 nm after the reaction. The large metallic particles are supposed to contribute to the reaction as well as the fine Cu₂O particles although the surface area is estimated to be significantly smaller than that of the latter.     

Influence of Ca/Al Ratio on Properties of Amorphous/Nanocrystalline Cu–Al–Ca–O Thin Films

This article reports the characterization of thin films sputtered from CuAl_1?xCa_xO targets (x = 0, 0.05, 0.1, 0.15, and 0.2) at room temperature. All films exhibit amorphous/nanocrystalline structures. Their transparency increases slightly with the addition of Ca. Furthermore, the resistivity decreases as the Ca/Al atomic ratio increases. Transmission electron microscopy with energy dispersive spectroscopy mapping indicates that the composition is uniform throughout the films deposited from the highest Ca doping concentration target. Some nanocrystals are present at the top surface of the CuAl_0.8Ca_0.2O thin film as well as the interface region between the CuAl_0.8Ca_0.2O thin film and the glass substrate, whereas the interior of the film is pretty amorphous with some embedded nanocrystals. X‐ray photoelectron spectroscopy shows that the Cu²⁺/Cu⁺ atomic ratio increases with the Ca/Al atomic ratio, indicating the enhancement of p‐type conductivity from the nonisovalent Cu–O alloying.     

Critical Evaluation and Thermodynamic Modeling of the MgO–MnO–Mn2O3–SiO2 System

A complete literature review, critical evaluation, and thermodynamic optimization of phase diagrams and thermodynamic properties of the MgO–MnO–Mn₂O₃–SiO₂ system at 1 atm pressure are presented. The molten oxide phase was described by the Modified Quasichemical Model considering the short‐range ordering in molten oxide, and the Gibbs energies of solid solutions were described using the Compound Energy Formalism considering the crystal structure of each solid solution. A set of optimized model parameters of all phases was obtained which reproduces all available and reliable thermodynamic data and phase diagrams within experimental error limits from 25°C to above the liquidus temperatures over the entire range of composition under the oxygen partial pressures from metallic saturation to 1 atm. The database of the model parameters can be used along with software for the Gibbs energy minimization to calculate any phase diagram section and thermodynamic property within the present system.     

Syntheses of Spinon Thermal Conductivity Materials in Sr–Cu–O System by Glass‐Ceramics Technique

We have synthesized spinon thermal conductivity materials in Sr–Cu–O system by glass‐ceramics technique. The materials are promising for active control of thermal energy in microelectronic devices because of high and anisotropic thermal conduction, its controllability, and electric insulation. Nevertheless, research on these materials has been limited to that concerning theoretical perspectives and investigation of physical properties using large single crystals. In this study, we adopt glass‐ceramics technique to synthesize these materials: We prepared melt‐quenched multicomponent oxides including SrO and CuO, and checked its glass‐forming ability and crystallization behaviors by heating. As a result, we have found that SrCuO₂ and Sr₁₄Cu₂₄O₄₁, known as the spinon thermal conductivity materials, are synthesized using SrO–CuO–?Li₂O–?Al₂O₃?–Ga₂O₃ system. This synthesis process for the system will provide practical application of the spinon thermal conductivity materials.     

A Coated Infiltration Growth Technique for Fabricating Single‐Grain Y–Ba–Cu–O Bulk Superconductor

A coated infiltration growth technique was proposed to fabricate single‐grain Y?Ba?Cu?O bulk superconductor, in which a liquid source coated Y₂BaCuO₅ (Y‐211) preform was employed and the liquid source composition was 3BaO + 5CuO. Experimental results indicated that, the sample exhibited a single‐grain morphology on the top surface, and the liquid source coating always existed surrounding the bulk which contributed to the complete growth of the sample. The homogeneous distribution of fine Y‐211 inclusions in microstructure and a satisfactory J_c performance of 5.67 × 10⁴ A/cm² in self‐field at 77 K have also been observed.     

Thermal conversion synthesis of Cu2O photocathode and the promoting effects of carbon coating

Simplifying the synthesis of cuprous oxide (Cu₂O) photocathode has turned out to be critical for scalable application. Herein, we present a novel thermal conversion approach to synthesize a shell/core structured Cu₂O/Cu photocathode. In this method a shell comprising a mixture of CuO and Cu₂O is obtained by heating Cu mesh at 500 °C in air beforehand, and subsequent annealing in N₂ atmosphere converts the unwanted CuO into Cu₂O gradually, which results in the desired Cu₂O/Cu structure. A slightly viscous starch sol coats the Cu₂O shell as carbon source, after carbonizing under N₂ atmosphere, the Cu₂O/Cu is covered with compact carbon films, i.e. C/Cu₂O/Cu. Photoelectrochemical experiments reveal that the introduction of carbon layers on Cu₂O enhances the photocurrent density from − 1.5 to − 2.75 mA·cm^− 2 at 0 V vs. reversible hydrogen electrode (RHE). Moreover, the deposition of carbon films on Cu₂O in this work has little effect on improving the stability.     

Characterizations of TiO2/SiO2/Ni–Cu–Zn Ferrite Composite for Magnetic Photocatalysts

The TiO₂/SiO₂/Ni–Cu–Zn ferrite composite for magnetic photocatalysts with high photocatalytic activity is successfully prepared in this study. The composite are composed of spherical or elliptical Ni–Cu–Zn ferrite nanoparticles about 20–60 nm as magnetic cores, silica as barrier layers with thickness of 15 nm between the magnetic cores and titania shells with thickness approximately 1.5 nm. Photodegradation examination of TiO₂/SiO₂/ Ni–Cu–Zn ferrite composite was carried out in methylene blue (MB) solutions illuminated under a Xe arc lamp with 35 W and color temperature of 6000 K. The results indicated that about 47.1% of MB molecules adsorbed on the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite within 30 min mixing due to it higher pore volume of 0.034 cm³/g, and after 6 h Xe lamp irradiation, 83.9% of MB 16.1% was photodegraded. Compared with the TiO₂ /Ni–Cu–Zn ferrite composite, the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite with silica barrier layer prohibited the photodissolution and enhanced the photocatalytic ability. The magnetic photocatalyst shows high photocatalytic efficiency that the apparent first‐order rate constant k_obs is 0.18427 h^?1, and good magnetic property that the saturation magnetization (M_s) of is 37.45 emu/g, suggesting the magnetic photocatalyst can be easily recovered by the application of an external magnetic field.     

Experimental phase equilibria studies of the PbO–SiO2 system

Phase equilibria of the PbO–SiO₂ system have been established for a wide range of compositions: (i) liquid in equilibrium with silica polymorphs (quartz, tridymite, and cristobalite) between 740°C and 1580°C, at 60‐90 mol% SiO₂; (ii) with lead silicates (PbSiO₃, Pb₂SiO₄, and Pb₁₁Si₃O₁₇) and lead oxide (PbO) between 700°C and 810°C. A high‐temperature equilibration/quenching/electron probe X‐ray microanalysis (EPMA) technique has been used to accurately determine the compositions of the phases in equilibrium in the system. Significantly, no liquid immiscibility has been found in the high‐silica range, and the liquidus in this high‐silica region has been accurately measured. The phase equilibria information in the PbO–SiO₂ system is of practical importance for the improvement of the existing thermodynamic database of lead‐containing slag systems (Pb–Zn–Fe–Cu–Si–Ca–Al–Mg–O).     

Phase Evolution of SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2‐Based Glass with Added Y‐PSZ Particles

Yttria partially stabilized zirconia Y‐PSZ/glass‐ceramic composites were prepared by reaction sintering using powder mixtures of a SiO₂–Al₂O₃–ZnO–CaO–ZrO₂–TiO₂‐based glass and yttria partially stabilized zirconia (Y‐PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass‐ceramic matrix for high‐temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass‐ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid‐like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass‐ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y‐PSZ/glass‐ceramic composites.     

Frequency and Temperature‐Independent Electrical Transport Properties of 2BaO–0.5Na2O–2.5Nb2O5–4.5B2O3 Glass‐Ceramics

The temperature (300–973 K) and frequency (100 Hz–10 MHz) response of the dielectric and impedance characteristics of 2BaO‐0.5Na₂O–2.5Nb₂O₅–4.5B₂O₃ glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100 Hz–10 MHz) and temperature (300–600 K). The temperature coefficient of dielectric constant was 8 ± 3 ppm/K in the 300–600 K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal‐glass interface, leading to a high value of effective dielectric constant especially for the samples heat‐treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P_r) increased with the increase in crystallite size.