Spectroscopic Properties of Er3+-Doped Na2O–La2O3–Al2O3–SiO2 Glasses

Er³⁺-doped sodium lanthanum aluminosilicate glasses with compositions of (90− x )(0.7SiO₂·0.3Al₂O₃)· x Na₂O·8.2La₂O₃· 0.6Er₂O₃·0.2Yb₂O₃·1Sb₂O₃ (in mol%) ( x = 12, 20, 24, 40, 60 mol%) were prepared and their spectroscopic properties were investigated. Judd–Ofelt analysis was used to calculate spectroscopic properties of all glasses. The Judd–Ofelt intensity parameter Ω _t ( t = 2, 4, 6) decreases with increasing Na₂O. Ω₂ decreases rapidly with increasing Na₂O while Ω₄ and Ω₆ decrease slowly. Both the fluorescent lifetime and the radiative transition rate increase with increasing Na₂O. Fluorescence spectra of the ⁴ I _13/2 to ⁴ I _15/2 transition have been measured and the change with Na₂O content is discussed. It is found that the full width at half-maximum decreases with increasing Na₂O.     

Al2O3–ZrO2–SiO2 Ternary Glasses for Molybdenum Oxidation Barriers

The wettability of binary and ternary glasses belonging to SiO₂–Al₂O₃–ZrO₂ diagram has been studied using the sessile drop technique at 1750° and 1800°C. The ternary SiO₂–Al₂O₃–ZrO₂ (90–5–5 wt%) glass has proved to be well appropriated as a molybdenum oxidation barrier coating. The addition of 5 wt% of MoO₂ slightly improves its wettablity at higher temperatures without affecting its oxidation barrier properties. The Mo comes into the glass network as a mixture of Mo⁵⁺, Mo⁴⁺, and Mo⁶⁺. After oxidation at 1000°C in oxygen atmosphere, the molybdenum remains in the glass network as Mo⁶⁺.     

Effect of Sb2O3 on Thermal Properties of Glasses in Bi2O3–B2O3–SiO2 System

Glasses with compositions 50Bi₂O₃– x Sb₂O₃–10B₂O₃–(40– x ) SiO₂ ( x =0, 1, 3, 5, 8, 10) have been prepared by conventional melt quench technique. Substitution of Sb₂O₃ for SiO₂ exerted an obvious effect on properties of glasses, especially, increased glass transition temperature ( T _g) and crystalline temperature ( T _c) greatly. Results of infrared transmission spectra attributed the effect to the formation of new bridging bonds of Sb–O–B and Sb–O–Si in glass network.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Vaporization Studies of the La2O3–Ga2O3 System

The vaporization of the samples of the compositions Ga₂O₃+ LaGaO₃, LaGaO₃+ La₄Ga₂O₉, and La₄Ga₂O₉+ La₂O₃ was investigated using Knudsen effusion mass spectrometry in the temperature range 1494–1937 K. The partial pressures of the gaseous species O₂, Ga, GaO, Ga₂O, and LaO were determined over the samples investigated. The equilibrium partial pressures were used for the calculation of the thermodynamic activities of the components at 1700 K. Gibbs energies of formation of LaGaO₃( s ) and La₄Ga₂O₉( s ) at 1700 K from the component oxides were derived from the thermodynamic activities as −46.4 ± 4.7 and −99.2 ± 7.9 kJ·mol⁻¹, respectively. The results were compared with the literature data obtained using other methods.     

The System SiO2–P2O2

Phase relations in the binary system between SiO₂-P₂O₅ and SiO₂ were investigated by the quenching method using sealed platinum tubes to prevent the loss of P₂O₅. The compound Si0₂-P₂O₅ exists in two forms, the low-temperature β form inverting sluggishly but reversibly to the high-temperature β form at 1030°C. The β form melts congruently at 1290°C. The compound 2SiO₂-P₂O₅ melts incongruently at 1120°C to a silica-rich liquid and SiO_a-P₂O₅. In the region between 5 and 25 mole % PO₂, reactions were so sluggish that no data could be obtained by quenching.     

Investigation on the Microstructure and Dielectric Properties of BaTiO3–Nb2O5–Fe2O3 Materials Doped with La2O3

The influence of La₂O₃ doped on the microstructure and dielectric properties, including the phase structure, temperature dependence of permittivity, and the hysteresis loop of BaTiO₃–Nb₂O₅–Fe₂O₃ (BTNF) materials has been investigated in X-ray diffraction, SEM, and LCR analyzer, respectively. Experiments revealed that incorporation of proper content of La₂O₃ basically soluted in the lattice of BaTiO₃ and can control the grain-growth, reduce the dielectric loss of the BTNF materials. The development of microstructure promoted by the additives can result in the improvement of the dielectric constant. When the doping concentration of La₂O₃ was 3.846 wt%, the relative dielectric constant of the sample sintered at 1280°C only for 2 h could reach 4308, and improve the dielectric-temperature characteristics markedly. As a result, a novel Y5P can be achieved in the BTNF ceramics, which is very promising for practical use in Y5P multilayer ceramic capacitors.     

Determination of CaO–SiO2–MgO–Al2O3–CrOx Liquidus

In this work, the liquidus of synthetic CaO–SiO₂–MgO–Al₂O₃–CrO _x slags is evaluated in the industrially relevant compositional domain. Equilibrium experiments are carried out at 1500°C and partial oxygen pressure ( p _O2) 10^−11.04 atm, and at 1600°C and p _O2=10^−10.16 and 10^−9.36 atm. The studied basicities (CaO/SiO₂) are 1.2 and 0.5. Al₂O₃ levels range from 0 to 30 wt%. Oversaturated liquid is sampled and phase relations are measured with quantitative electron probe microanalysis–wavelength dispersive spectroscopy (EPMA–WDS). The results are compared with the commercially available FactSage thermodynamic databases. Qualitative agreement is always obtained. Also a good quantitative agreement is found at the higher basicity, especially for the spinel liquidus. A minor but systematic deviation can be observed for the eskolaite liquidus. At the lower basicity, the calculated phase diagram deviates strongly from the experimental results, probably due to missing ternary interactions in the database.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

Phase Equilibria in the System HfO2–Y2O3–CaO

Phase equilibria in the system HfO₂–Y₂O₃–CaO were studied in the temperature range 1250° to 2850°C by both experimental methods (X-ray phase analysis at 20° to 2000°C, petrography, annealing and quenching, differential thermal analysis in He at temperatures to 2500°C, thermal analysis in air using a solar furnace at temperatures to 3000°C, and electron microprobe X-ray analysis) and theoretical means (development of a mathematical model for the liquidus surface by means of the reduced polynomial method). Phase equilibria were determined by the structure of the restricting binary systems. No ternary compounds were found. The liquidus was characterized by the presence of six four-phase, invariant equilibria. Solid solutions were based on monoclinic (M), tetragonal (T), and cubic (F) modifications of HfO₂; C and H forms of Y₂O₃; CaO; and CaHfO₃ that crystallized in two polymorphous modifications, namely, the cubic and rhombic perovskite-type structure.     

Phase Relations In The Pseudo-Ternary System La2O3–SrO–Fe2O3

The phase relations in the pseudo-ternary system La₂O₃–SrO–Fe₂O₃ have been investigated in air. Isothermal sections at 1100° and 1300°C are presented based on X-ray diffraction and thermal analysis of annealed samples. Extended solid solubility was observed for the compounds Sr _{n +1− v} La _v Fe _n O_{3 n +1−δ} ( n =1, 2, 3, and ∞) and Sr_{1− x} La _x Fe₁₂O₁₉, while only limited solubility of La in Sr_{4− z} La _z Fe₆O_13±δ was observed. At high Fe₂O₃ content, a liquid with low La₂O₃ content was stable at 1300°C.     

Rapid Crystallization of SiO2-Al2O3 Glasses

The crystallization of Al₂O₃-rich glasses in the system SiO₂-Al₂O₃ which were prepared by flame-spraying and/or splat-cooling was studied by DTA, electron microscopy, and X-ray diffraction. Over a wide range of compositions, the crystallization temperature ( T_x ) remained near 1000°C, changing smoothly with composition. In all cases crystallization of mullite was detected by X-ray diffraction. In the low-Al₂O₃ region, coarsening of the microstructure during crystallization was observed by electron microscopy. In the high-Al₂O₃ region mullite and γ-Al₂O₃ cocrystallized; this behavior may be interpreted as evidence of a cooperative process of crystallization at the respective T_x 's. The crystallite size of the mullite immediately after rapid crystallization increased continuously with increasing Al₂O₃ content. In light of the T_x data, the adequacy of the evidence for the proposed metastable miscibility gap in the SiO₂-Al₂O₃ system is questioned.     

Effect of Cr2O3 on Slag Resistance of Al2O3–SiO2 Refractories

Refractory bodies of 65 wt% Al₂O₃ were prepared from a mixture of calcined alumina and raw kaolin with the addition of Cr₂O₃ up to 15 wt%. The Cr₂O₃ addition effectively enhances slag resistance and reduces mullite formation. Petrographic analysis of the refractories after the slag test suggests that Cr₂O₃ increases the viscosity of both the glassy phase in the refractory as well as the slag, thereby retarding slag penetration and reaction at elevated temperature.     

Influence of SO3 on the Phase Relationship in the System CaO–SiO2–Al2O3–Fe2O3

The influence of the additive SO₃ on the phase relationships in the quaternary system CaO-SiO₂-Al₂O₃-Fe₂O₃ was investigated by observing the change of volume ratio of 3CaOSiO₂ (C₃S) to 2CaOSiO₂ (C₂S) + CaO (C) in the sintered material with the increase of SO₃ content. The primary phase volume of C₃S in the quaternary phase diagram shrank with the increase of SO₃ and disappeared when the SO₃ content exceeded 2.6 wt% in the sintered material. Changes in the peritectic reaction relationship between CaO (C), 2CaOSiO₂ (C₂S), 3CaOSiO₂ (C₃S), 3CaOAl₂O₃ (C₃A), 4CaOAl₂O₃Fe₂O₃ (C₄AF), and liquid were also observed and discussed.     

Structural Analysis of SiO2-Al2O3 Glasses

The structure of SiO₂-Al₂O₃ glasses with up to 60 wt% Al₂O₃ was investigated using the radial distribution function together with the correlation method based on X-ray scattering intensity data. Radial distribution curves are interpreted on the basis of glass-in-glass separation with the constituents of SiO₂-rich and Al₂O₃-rich glasses. The structure of the Al₂O₃-rich glass has a short-range ordering similar to the crystal structure of mullite. The calculated S- i (S) curve of this model gives good agreement with the observed one.     

Phase Equilibrium Relationships at Liquidus Temperatures in the System FeO–Fe2O3–Al2O3–SiO2

Phase equilibrium data at liquidus temperatures are presented for mixtures in the system FeO–Fe₂O₃–Al₂O₃–SiO₂. The volume located between the 1 and 0.2 atm. O₂ isobaric surfaces of the tetrahedron representing this system was studied in detail. Scattered data were obtained at lower O₂ pressures. Results obtained in the present investigation were combined with data in the literature to construct a phase equilibrium diagram, at liquidus temperatures, for the entire system FeO–Fe₂O₃–Al 2 O₃–SiO₂. Methods for interpretation of the diagram are explained.     

Phase Equilibria in the System NiO–Al2O3–SiO2

Equilibrium diagrams for the systems NiO-SiO₂, NiO-Al₂O₃, NiAl₂O₄-SiO₂, Ni₂SiO₄-NiAl₂O₄, and NiAl₂O₄-Al₆Si₂O₁₃ were drawn from data obtained by quenching and direct observational techniques. The only intermediate compound in the binary system NiO-SiO₂ is Ni₂SiO₄, which has the olivine structure. Unlike other olivines which melt congruently, nickel olivine has an upper temperature of stability (1545°C) and at temperatures between 1545° and 1650°C, NiO and SiO₂ coexist in equilibrium. The only compound in the binary system NiO-Al₂O₃ is NiAl₂O₄, which has a spinel structure. The nickel aluminate spinel varies in composition from 50 to 35 mole % Al₂O₃ at 1800°C, and the stoichiometric NiAl₂O₄ composition has a melting point near 2110°C. Of the joins within the ternary system NiO-Al₂O₃-SiO₂ which were studied, only Ni₂SiO₄-NiAl₂O₄ is not binary. In this join, crystals of NiO exist in equilibrium with liquid and a ternary assemblage of NiO + NiAl₂O₄+ liquid is stable to 1775°C. The decomposition temperature of Ni₂SiO₄ is decreased from 1545°C in the binary system to approximately 1490°C, presumably the result of solubility of NiAl₂O₄ in Ni₂SiO₄. The join NiAl₂O₄-SiO₂ is binary in that the compositions of crystalline phases can be expressed in terms of the chosen components. The eutectic temperature in the system is 1495°C. The join NiAl₂O₄-Al₆Si₂O₁₃ is binary for the same reasons and has a eutectic temperature at 1720°C. Using the data obtained in this study and those published for the well-known system Al₂O₃-SiO₂, a liquidus surface diagram for the system NiO-Al₂O₃-SiO₂ is proposed. Nickel olivine, even though it has an upper limit of stability in the binary system, has a primary field in the ternary system NiO-Al₂O₃-SiO₂. This is the only refractory oxide system known to illustrate this so-called “typical case,” the governing principles of which have been clearly presented in discussions of phase equilibria.