Effect of TiO2 addition amount on BaO–CaO–Al2O3 -SiO2 glass-bonded Al2O3 ceramics

A new type of glass-ceramic BaO–CaO–Al₂O₃–SiO₂ (BCAS) was developed to join Al₂O₃ ceramics, adding TiO₂ to the glass-ceramics can promote the crystallization behavior of the glass-ceramics. Through the observation of the joints, rutile TiO₂ whiskers can grow on the surface of Al₂O₃ ceramics, and the grown TiO₂ whiskers are one-dimensional needle-like whiskers growing in different directions in the joints, providing mechanical support for the joints. The aspect ratio of TiO₂ whiskers was changed by controlling the addition of TiO₂, and the crystallization behavior and microstructure of the joints were studied. The experimental results show that when the amount of TiO₂ added is 10% (wt%), the density of TiO₂ whiskers in the joint is the largest, the strengthening effect on the joint is the best, and the shear strength can reach 94.33 MPa.     

Application of BaO–CaO–Al2O3–B2O3–SiO2 glass–ceramic seals in large size planar IT-SOFC

BaO–CaO–Al₂O₃–B₂O₃–SiO₂ (BCAS) glass–ceramics can be used as sealant for large size planar anode-supported solid oxide fuel cells (SOFCs). BCAS glass–ceramics after heat treatment for different times were characterized by means of thermal dilatometer, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the coefficients of thermal expansion (CTE) of BCAS glass–ceramics are 11.4×10⁻⁶ K⁻¹, 11.3×10⁻⁶ K⁻¹ and 11.2×10⁻⁶ K⁻¹ after heated at 750 °C for 0 h, 50 h, and 100 h, respectively. The CTE of BCAS matches that of YSZ, Ni–YSZ and the interconnection of SOFC. Needle-like barium silicate, barium calcium silicate and hexacelsian are crystallized in the BCAS glass after heat-treatment for above 50 h at 750 °C. The glass–ceramics green tape prepared by aqueous tape casting can be directly applied in sealing the cell of SOFCs with 10 cm×10 cm. The open circuit voltage (OCV) of the cell keeps 1.19 V after running for 280 h at 750 °C and thermal cycling 10 times from 750 °C to room temperature. The maximum power density is 0.42 W/cm² using pure H₂ as fuel and air as oxidation gas. SEM images show no cracks or pores exist in the interface of BCAS glass–ceramics and the cell.     

Antibacterial and photocatalytic active transparent TiO2 crystallized CaO–BaO–B2O3–Al2O3–TiO2–ZnO glass nanocomposites

Transparent TiO₂ crystallized 5CaO–10BaO–65B₂O₃–Al₂O₃–20TiO₂–10ZnO (CBBATZ) glass nanocomposites were fabricated using melt-quenching technique followed by specific heat treatments. As-quenched glass samples were provided three different heat treatments at 630°C for 3, 5, and 10 hours in order to obtain different amounts of TiO₂ nanocrystals in the glass. The presence of rutile phase of TiO₂ nanocrystals in glass was confirmed by X-ray diffraction. The glass nanocomposite heat treated for 10 hours showed a hydrophobic nature with contact angle of 90.90°. Contact angle decreased from 90.90 to 22.20°, when irradiated under ultraviolet (UV) radiation for 45 minutes. This photoinduced hydrophilicity showed a photocatalytic and self-cleaning properties of glass nanocomposite. During photocatalytic ink test, the maximum change in color of Resurin (Rz) ink and 60% degradation in absorbance of ink within 150 minutes under UV radiation were found for glass nanocomposite heat treated at 10 hours. Also, 78% degradation in absorbance of methylene blue dye (pollutant) within 180 minutes under UV irradiation was found for glass naocomposite heat-treated at 10 hours. Antibacterial performance of transparent glass nanocomposite against Escherichia coli was evaluated as well. More than 95% of the bacterial cells were degraded with glass nanocomposite heat-treated at 10 hours. CBBATZ glass nanocomposite found to impart the antibacterial effect through generation of reactive oxygen species (ROS) in aqueous medium. ROS species which was confirmed in the bacterial cell through intracellular ROS generation kit. During evaluation of mechanical properties using nanoindentation technique, the values of hardness and reduced modulus increased by ~26% and 10%, respectively, for glass nanocomposite heat-treated at 10 hours as compared to as-quenched glass.     

Dielectric Characteristics of Ceramics in BaO–Nd2O3–TiO2–Ta2O5 System

Dielectric ceramics in the BaO–Nd₂O₃–TiO₂–Ta₂O₅ system were prepared and characterized. The ceramics with tungsten–bronze structure based on the compositions Ba₂NdTi₂Ta₃O₁₅ and Ba₅NdTi₃Ta₇O₃₀ had a high dielectric constant (>100) with a lower frequency-dependency when complete densification was achieved; a low dielectric loss was obtained in the former.     

Dielectric Relaxation in CaO–Bi2O3–B2O3 Glasses

Glasses in the system CaO–Bi₂O₃–B₂O₃ (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond–West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent β (0.5–0.6) is invariant with temperature for the present glasses.     

Thermal and devitrification behavior of CaO–Ga2O3–SiO2 glasses

A study of the influence of the substitution of Ga₂O₃ for CaO, at constant O/Si ratio, on thermal properties and non-isothermal devitrification of 2.5CaO.2SiO₂ is reported. Differential thermal analysis (DTA) and X-ray diffraction analysis were used. The X-ray diffraction pattern of the crystallized Ga₂O₃ base glass shows that the αCaO SiO₂, that should be stable only above 1125°C, forms in the temperature range 900–1000°C. A new ternary crystalline phase, whose reflections are not reported in the JCPDS cards, was found to form during crystallization of the glass. The glass transformation temperature, T_g, and softening, T_s, temperature decrease as Ga₂O₃ is substituted for CaO. This is the result of the substitution of the network modifying cation Ca²⁺, of higher coordination number, by a network forming cation Ga³⁺ in fourfold coordination, in a composition range of relative insensitivity to changes of covalent cross-linking density. The crystal growth activation energy, E_c, decreases with substitution; this is the consequence of the decrease of the structural rigidity and of the shift of crystallization to a higher temperature range. Devitrification involves a mechanism of surface nucleation; surface nuclei behaving as bulk nuclei in samples that soften and sinter before devitryfing.     

Effect of varying Al2O3 contents of CaO–Al2O3–SiO2 slags on lumped MgO dissolution

This study utilized the single hot thermocouple technique to examine the dissolution behavior of lumped magnesium oxide (MgO) in CaO–Al₂O₃–SiO₂ ternary slags. The aluminum oxide (Al₂O₃) content in the slag (C/S = 1) varied from 10% to 30%; the MgO sphere with a diameter of 1 mm was placed in molten slags at 1,550 °C. Results showed that the dissolution rate decreased as the Al₂O₃ content increased up to 20%. Over 20% Al₂O₃, MgAl₂O₄ was formed at the interface of MgO and it did not fully melt at 30% Al₂O₃. The dissolution behavior and the formation of MgAl₂O₄ were analyzed by a phase diagram provided by Factsage 7.0 software. In the case of less than 20% Al₂O₃ content, apparent sphere radii were measured; the shrinking core model was then applied to understand the dissolution mechanism. The dissolution rate of both slags was controlled by boundary layer diffusion. The dissolution rate at 20% Al₂O₃ slag appeared to fit the behavior to the boundary layer diffusion, although it deviated during the middle stage of the dissolution because of MgAl₂O₄ formation. The 10% Al₂O₃ slag fitted well to the boundary layer diffusion curve; the obtained diffusion coefficient was 0.94 × 10⁻⁹ m²/s.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Stability in the system CaO–Al2O3–H2O

The solubility of AH₃, CAH₁₀, C₂AH_7.5, and C₃AH₆ was determined experimentally at 7 to 40 °C and up to 570 days. During the reaction of CA, at 20 °C and above initially C₂AH_7.5 formed which was unstable in the long-term. The solubility products calculated indicate that the solubilities of CAH₁₀, C₂AH_7.5 and C₄AH₁₉ increase with temperature while the solubility of C₃AH₆ decreases. Thus at temperatures above 20 °C, C₃AH₆ is stable, while at lower temperature also CAH₁₀ and C₄AH₁₉ are stable, depending on the C/A ratio.At early hydration times, CAH₁₀ can be stable initially at 30 °C and above, as the formation of amorphous AH₃ stabilises CAH₁₀ with respect to C₃AH₆ + 2AH₃. With time, as the solubility AH₃ decreases due to the formation of microcrystalline AH₃, CAH₁₀ becomes unstable at 20 °C and above.     

Effect of CaO doping on the properties and crystallization behavior of Y2O3–Al2O3–SiO2 glass

Nowadays, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass joining is considered to be a promising scheme for nuclear-grade continuous silicon carbide (SiC) fiber reinforced SiC matrix composites (SiC/SiC). CaO has great potential for nuclear applications since it has low reactivity and low decay rate under nuclear irradiation. In this paper, the effect of CaO doping on the structure, thermophysical properties, and crystallization behavior of YAS glass was systematically studied. As the CaO doping content increased, the number of bridge oxygens and the viscosity at high temperatures reduced gradually. After heat treatment at 1400 °C, the main phases in YAS glass were β-Y₂Si₂O₇, mullite, and SiO₂ (coexistence of crystalline and glass phases), while that with 3.0% CaO doping turned into a single glassy phase under the same treatment conditions. Moreover, a structural model and the modification mechanism were proposed, which provided a theoretical basis for the subsequent component design and optimization.     

Corrosion of spinel clinker by CaO–Al2O3–SiO2 ladle slag

Three different grades of sintered spinel clinker were used containing 47, 69 and 94 wt.% Al₂O₃, respectively, i.e. MgO-rich, stoichiometric and Al₂O₃-rich. Based on these clinkers, the corrosion mechanism of each spinel clinker by CaO–Al₂O₃–SiO₂ slag was investigated and the corrosion and penetration behavior of castables containing powdered spinel clinker examined. A layer of MgO·(Al, Fe)₂O₃ complex spinel formed at the slag-refractory interface was proportional to the MgO content of the spinel clinkers, and it depressed the slag corrosion. The free MgO and spinel minerals in each spinel clinker mainly trapped Fe₂O₃ from the slag. CaO–Al₂O₃ compounds were formed at the slag-clinker interface by the reaction between free Al₂O₃ in the Al₂O₃-spinel clinker and CaO from slag. Slag penetration into the spinel clinkers was retarded by these compounds. As a result of adding fine spinel powder to the matrix of Al₂O₃-based castables, it was observed that higher content of MgO in spinel clinker showed better resistance to slag corrosion but lower resistance to slag penetration.     

Energy Transfer and Spectroscopic Investigation of Dy2O3 Doped Li2O–BaO–GdF3–SiO2 for White Light LED

Glass Physics and Chemistry - LGFDy glasses doped with Dy2O3 (0.1, 0.5, 1.0, 1.5 and 2.0 mol %) were synthesised by conventional melt quenching method and various properties are studied by...     

Effects of La2O3–B2O3 on the flexural strength and microwave dielectric properties of low temperature co-fired CaO–B2O3–SiO2 glass–ceramic

The La₂O₃–B₂O₃ (LB) addition, synthesized using the traditional solid-state reaction process, was chosen as a novel sintering aid of the low temperature co-fired CaO–B₂O₃–SiO₂ (CBS) glass–ceramic. The effects of LB on the flexural strength and microwave dielectric properties have been investigated. The LB addition promotes the crystallization of the CaSiO₃ but high amount of the LB addition leads to the formation of more pores. The CBS sample with 4 wt% LB addition sintered at 850 °C for 15 min shows good properties: flexural strength = 193 MPa, ?_r = 6.26 and loss = 9.96 × 10^?4 (10 GHz).     

Thermodynamics and crystallization kinetics of REEs in CaO–SiO2–Ce2O3 system

Rare earth elements (REEs) have become increasingly important as ceramic materials. The RE-bearing slags contain massive REEs resources, whereas the lack of thermodynamic and kinetic data of REEs has brought great difficulties to efficient recovery of REEs from RE-bearing slags and the application in ceramics. According to the compositions of the RE-bearing slags in industrial production, the isothermal phase equilibria of CaO–SiO₂–Ce₂O₃ system at 1500°C and 1300°C were constructed by means of liquid-quenching method combined with a series of analyses, which provides the thermodynamic data for the equilibria of REEs. On this basis, the crystallization behaviors of the RE phase (Ce_9.33−xCa_x(SiO₄)₆O_2−0.5x) was investigated, and the temperature range in which the RE phase crystallized singly in RE-bearing slags with a selected compositions was acquired. CCT and TTT diagrams for CaO–SiO₂–Ce₂O₃ system were established to characterize the crystallization kinetics of the RE phase, and the favorable conditions for its crystallization and growth in RE-bearing slags were determined. In this study, the complete thermodynamic and kinetic basic data of REEs in CaO–SiO₂–Ce₂O₃ system are provided for RE-bearing slags.     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

Phase equilibria studies in the CaO–SiO2–Al2O3–MgO system with CaO/SiO2 ratio of 0.9

Phase equilibria and liquidus temperatures in the CaO–SiO₂–Al₂O₃–MgO system at a CaO/SiO₂ weight ratio of 0.9 in the liquid phase have been experimentally determined employing high-temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Isotherms at 1573, 1623, 1673, and 1773 K were determined and the primary phase fields of wollastonite, melilite, olivine, periclase, spinel, and corundum have been located. Compositions of the olivine and melilite solid solutions were analyzed and discussed. Comparisons between the newly constructed diagram, existing data, and FactSage predicted phase diagrams were performed and differences were discussed. The present study will be useful for guidance of industrial practices and further development of thermodynamic modeling.     

Effect of fluorine and CaO/Al2O3 mass ratio on the viscosity and structure of CaO–Al2O3-based mold fluxes

The effect of CaO/Al₂O₃ mass ratio (C/A) and fluorine content on the viscosity and structure of CaO–Al₂O₃-based mold fluxes has been researched in this paper. The viscosity results indicated that increasing fluorine only slightly decreases the viscosity of the slag melt, and higher C/A is also observed to decrease the viscosity of molten slag when the C/A changes from 1.3 to 1.7. Structural analysis of the as-quenched fluxes using the Raman spectroscopy showed that the amounts of Al–O⁰ and Si–O–Al structural units all decrease with higher fluorine content and C/A, indicating that a depolymerization of the molten structure is occurring. The results of ²⁷Al and ¹⁹F magic angle spinning nuclear magnetic resonance showed that fluorine tends to participate in the network structure and coordinate with Al³⁺ ions to form complex ionic clusters. The results suggested that the role of fluorine in the CaO–Al₂O₃-based slag system is different from the traditional slag system in which fluorine only acts as a diluent, thus reducing the effect of fluorine on lowering the viscosity. In addition, the coordination environment of Al³⁺ ions can be simplified by higher C/A through promoting the generation of [AlO₄]⁻ tetrahedral structures. Besides, the free O²⁻ ions provided by excess CaO would break the Al–O⁰ bonds and further depolymerize the network structure, thereby decrease the viscosity.     

Effect of spray process on dielectric properties of APS-deposited CaO–B2O3–SiO2 glass-ceramic coatings

Low-dielectric properties are highly desirable for successful realization of thermal spray coatings in electromagnetic wave absorption. Herein, CaO–B₂O₃–SiO₂ (CBS) glass-ceramic coatings are prepared via high-enthalpy atmospheric plasma spraying (HE-APS) method, and the influence of spraying power on physical and dielectric properties of APS-deposited CBS coatings is systematically investigated. Under high-power conditions, the increase in liquid phase hinders the discharge of gases and leads to an increase in the porosity of CBS coatings. The experimental results reveal that the coating density decreases and coating porosity increases with the increase of spraying power. Based on the crystallization behavior of CBS coatings, an excellent low-dielectric crystalline phase (β-CaSiO₃) was obtained after heat treatment at 800 °C. According to the dielectric mixing rule of composite materials, the density and permittivity exhibit the same trend and a minimum permittivity of 5.74 is obtained.     

Ionic conductivity of CaO–Y2O3–ZrO2 materials with constant oxygen vacancy concentration

Structural modification of the fully stabilised zirconia is a possible way to improve its electrical properties. Electrical properties, especially ionic conductivity, of cubic zirconia solid solutions are strictly related to the ionic radius and valency of cations incorporated into the zirconia structure. Nanopowders with a constant oxygen vacancy concentration of 8 and 10 mol% were prepared by a hydrothermal treatment of co-precipitated zirconia hydrogels in a NaOH environment. The desired oxygen vacancy concentrations were obtained by introducing calcia and yttria, at different ratios, to the zirconia solid solutions. Phase compositions and lattice parameters of the respective phases were determined using X-ray diffraction analysis. Electrical properties of the samples were described on the basis of complex impedance spectroscopy analysis. It has been stated that substitution of calcia for yttria or yttria for calcia in zirconia solid solutions leads to ionic conductivity enhancement. Samples with a cubic structure, close to the stabilisation threshold, had the highest conductivity.     

3D microstructure and crack pathways of toughened CaO–Al2O3–SiO2 glass by precipitation of hexagonal CaAl2Si2O8 crystal

We investigated CaO–Al₂O₃–SiO₂ glass partially crystallized with molybdenum particles as nucleating agents. Microstructure of the material was characterized as a house-of-cards structure composed of plate-like crystals. Microcracks propagated along the crystal plane parallel to the double layer of SiO₄/AlO₄ tetrahedrons separated by layers of calcium atoms. To investigate the fracture behavior of the hexagonal CaAl₂Si₂O₈ crystals, molecular dynamics simulations were performed, which demonstrated that a crack can be easily triggered by shear deformation along the calcium layer. Additionally, once a crack was generated in the calcium layer, it propagated rapidly, whereas the crack perpendicular to the calcium layer hardly propagated. This simulated behavior is consistent with the experimentally observed cleavage behavior of the hexagonal CaAl₂Si₂O₈ crystal. The experimental and simulation results effectively explained the non-elastic fracture behavior of the material.