Preparation of Larnthanum β-Alumina with High Surface Area by Coprecipitation

Mixtures of La₂O₃ and Al₂O₃ with various La contents were prepared by co-precipitation from La(NO₃)₃ and Al(NO₃)₃ solutions and calcined at 800° to 1400°C. The addition of small amounts of La₂O₃ (2 to 10 mol%) to Al₂O₃ gives rise to the formation of lanthanum β-alumina (La 2 O₃·11–14Al₂O₃) upon heating to above 1000°C and retards the transformation of γ-Al₂O₃ to α-Al₂O₃ and associated sintering.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

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.     

Microstructure Characterization of the (1−x)La2/3TiO3·xLaAlO3 System

Microstructural characterizations on the (1− x )La_2/3TiO₃· x LaAlO₃ (LTLA) system were conducted using transmission electron microscopy. The presence of La₂Ti₂O₇ and La₄Ti₉O₂₄ phases in pure La_2/3TiO₃ is confirmed by the electron diffraction pattern. When x = 0.1, the ordering due to the A-site vacancies could be confirmed by the presence of antiphase boundaries (APBs) and return ½(100) superlattice reflection. As x increases, the ordering decreases and finally disappears when x = 0.6. The tilting of oxygen octahedra could be demonstrated by the presence of the ferroelastic domains in the matrix and return ½(111) and return ½(110) superlattice reflections in selected area electron diffraction patterns. In pure LaAlO₃, only the antiphase tilting of oxygen octahedra is present due to the presence of return ½(111) superlattice reflection. In the LTLA system of x = 0.1, both the antiphase and in-phase tiltings of the oxygen octahedra are involved; however, in the range of x from 0.3 to 0.9, the antiphase tilting of oxygen octahedra has appeared. The growth of the ferroelastic domains is influenced by the APBs in the matrix.     

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.     

Phases in the Binary Systems PbO—La2O3, Gd2O3, and Sm2O3

In the binary system PbO–La_zO₃ only one compound, 4PbO.La₂O₃, exists; it is flanked by two eutectics. The structure of the compound, although of lower symmetry, is intimately related to the C modification of the rare earths. Below 800° to 1000°C, metastable solid solutions are formed from oxide mixtures coprecipitated from mixed solutions of the nitrates, the cubic parameter a = 5.66 A, if extrapolated to pure La₂O₃, corresponding to half the a parameter of the C form of La₂O₃. The solid solutions existing between the compositions La₂O₃–2Pb0 and pure La₂O₃ have a cubic face–centered lattice and obey Vegard's rule. The systems of PbO with Sm₂O₃ and Gd₂O₈ are quite similar to that with La₂O₃. The compound Sm₂O₃.4Pb0 decomposes at 1000°C with evaporation of PbO; Sm₂O₃ remains in the B modification.     

Subsolidus Phase Relationships in the System Fe2O3–Al2O3–TiO2 between 1000° and 1300°C

Subsolidus phase equilibria in the system Fe₂O₃–Al₂O₃–TiO₂ were investigated between 1000° and 1300°C. Quenched samples were examined using powder X-ray diffraction and electron probe microanalytical methods. The main features of the phase relations were: (a) the presence of an M₃O₅ solid solution series between end members Fe₂TiO₅ and Al₂TiO₅, (b) a miscibility gap along the Fe₂O₃–Al₂O₃ binary, (c) an α-M₂O₃( ss ) ternary solid-solution region based on mutual solubility between Fe₂O₃, Al₂O₃, and TiO₂, and (d) an extensive three-phase region characterized by the assemblage M₃O₅+α-M₂O₃( ss ) + Cor( ss ). A comparison of results with previously established phase relations for the Fe₂O₃–Al₂O₃–TiO₂ system shows considerable discrepancy.     

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.     

Strength and Phase Stability of Yttria-Ceria-Doped Tetragonal Zirconia/Alumina Composites Sintered and Hot Isostatically Pressed in Argon–Oxygen Gas Atmosphere

Yttria-ceria-doped tetragonal zirconia (Y,Ce)-TZP)/alumina (Al₂O₃) composites were fabricated by hot isostatic pressing at 1400° to 1450°C and 196 MPa in an Ar–O₂ atmosphere using the fine powders prepared by hydrolysis of ZrOCl₂ solution. The composites consisting of 25 wt% Al₂O₃ and tetragonal zirconia with compositions 4 mol% YO_1.5–4 mol% CeO₂–ZrO₂ and 2.5 mol% YO_1.5–5.5 mol% CeO₂–ZrO₂ exhibited mean fracture strength as high as 2000 MPa and were resistant to phase transformation under saturated water vapor pressure at 180°C (1 MPa). Postsintering hot isostatic pressing of (4Y, 4Ce)-TZP/Al₂O₃ and (2.5Y, 5.5Ce)-TZP/Al₂O₃ composites was useful to enhance the phase stability under hydrothermal conditions and strength.     

Mechanochemical Synthesis of Lanthanum Aluminate by Grinding Lanthanum Oxide with Transition Alumina

Grinding lanthanum oxide (La₂O₃) with Al₂O₃ was conducted to investigate their mechanochemical reactions to form lanthanum aluminate (LaAlO₃) powder using a planetary ball mill. Grinding for 120 min allowed us to obtain single-phase LaAlO₃ with a large surface area when transition alumina was used, whereas no formation of LaAlO₃ was achieved when α-Al₂O₃ was used. The mechanochemical process can be applied to synthesize other rare-earth (RE) aluminates (REAlO₃) from mixtures of a rare-earth oxide and transition alumina.     

Polyhedral Arrangements in Lanthanum Aluminoborate Glasses

We have used magic-angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy to examine the polyhedral arrangements in ternary lanthanum aluminoborate glasses. We have characterized two glass-forming series: _x Al₂O₃·(1− x )LaB₃O₆ and 0.25La₂O₃· y Al₂O₃(1− y )-B₂O₃. ¹¹B MAS NMR reveals a decrease in the fraction of four-coordinated boron atoms with increases in the Al₂O₃ content in both series. ²⁷Al MAS NMR has detected four-, five- and six-coordinated aluminum atoms in complex aluminoborate networks similar to those reported elsewhere for alkaline-earth aluminoborate glasses. Raman spectroscopy reveals a variety of borate and aluminoborate moieties, including isolated groups as well as methaborate chains and rings. These results indicate that the La³⁺ ion acts as a modifier to the aluminoborate network.     

Magnetoplumbite-Corundum Phase Equilibria in the System Sr─Fe─Al─O at 1100°C

The phase relations in the region of the Fe₂O₃- and Al₂O₃-rich sides of the quaternary system SrO─Fe₂O₃–Al₂O₃–B₂O₃ and the location of conjugation lines between magnetoplumbite solid solution SrO·(6 − x)Fe₂O₃·xAl₂O₃ and corundum (α-Fe₂O₃, α-Al₂O₃) phases were determined at 1100°C in air by using the flux-growth method based on the Ostwald ripening mechanism. Activity–composition relations and the lattice parameters along the magnetoplumbite solid solutions were also obtained.     

Humidity-Sensitive Characteristics of Porous La-Ti-V-O Glass-Ceramics

The humidity-sensitive characteristics of La₂O₃–TiO₂–V₂O₅ glass-ceramics were investigated as a function of additive amount of V₂O₅ to the precursor glass and the heating temperature of the glass to iduce phase separation. The microstructure of each glass-ceramic was strongly dependent upon the heating temperature. The specific impedance was lowered by increasing the amount of V₂O₅ additive. Among the elements studied, the LTV 2–2 element, which was prepared from as-cast glass, consisted of Na₂O:B₂O₃:La₂O₃: TiO₂: V₂O₅= 8.3:32.9:7.2:31.6:20.0 (molar ratio) after heating at 450°C for 12 h and subsequent leaching at 85°C for 24 h, and was found to be the most suitable material from the standpoint of humidity sensitivity, measurability, and response time.     

SiAlON Composites Containing Rare-Earth Melilite and Neighboring Phases

Sintering aids with a formulation of rare-earth (R) melilite solid solution M'(R) have been introduced to several SiAlON composites to obtain high-density bodies by pressureless and gas-pressure sintering. These compositions include ones along the Si₃N₄–R₂O₃:9AlN line, which contain no Al₂O₃ and are known to have excellent strength but very poor sinterability. Phase analysis and property (hardness, toughness, strength, and oxidation resistance) measurements reveal a complex set of structure–property–processing relationships that are composition-dependent. Of the most importance is the Al—O content in various phases, which is dictated by the starting composition as well as Al—O solubility in M'(R). This influences the sinterability, strength, and phase assemblage through the compositions of the intermediate liquid and the final β'-SiAlON. La₂O₃ is further established as an effective sintering aid that does not affect the equilibrium phase assemblage. Overall, M'(R) and La₂O₃ show promise as SiAlON sintering aids that allow high density to be achieved without compromising intrinsic mechanical and thermal properties.     

Phase Equilibrium Relationships in a Portion of the System MgO–Al2O3–2CaO·SiO2

The system MgO–Al₂O₃–2CaO·SiO₂ comprises a plane through the tetrahedron CaO–MgO–Al₂O₃–SiO₂. A total of 108 compositions were prepared having an alumina content below the line joining 2CaO·Al₂O₃SiO₂ (gehlenite) and MgO·Al₂O₃ (spinel). Quenching experiments were carried out on 96 of these compositions at temperatures up to 1590°C. Three binary eutectic systems and two ternary eutectic systems are described. Compositions on this plane are of significance in an investigation of the constitution of basic refractory clinkers made from Canadian dolomitic magnesites. They also concern the compositions of certain blast furnace slags.     

Thermal, Dielectric, and Optical Properties of Neodymium Borosilicate Glasses for Thick Films

Because of their thermal, dielectric, and optical properties, new glass compositions and thick-filmed transparent dielectrics containing neodymium oxide (Nd₂O₃) were studied as a source of purer images in plasma display panels. In the present study, PbO–B₂O₃–SiO₂ and PbO–B₂O₃–SiO₂–ZnO–Al₂O₃ were used as starting glass compositions, to which up to 25 wt% of Nd₂O₃ then was added. Increased amounts of Nd₂O₃ increased the glass transition temperature and dielectric constant of the bulk glasses and decreased the coefficient of thermal expansion. The fired thick films (around 30 μm) allowed selectively visible light to penetrate and showed deep absorption properties at 585 nm that were related to an extraneous gas from neon discharge.     

X-ray Diffraction and Microstructural Investigation of the Al2O3-La2O3-TiO2 System

The ternary phase diagram of Al₂O₃-La₂O₃-TiO₂ at 1400°C was determined with 12 compatibility triangles. Al₂O₃ stabilizes the A-site-deficient La_2/3TiO₃ perovskite structure. According to XRD and microstructural investigations, the solid solution extends along the La_2/3TiO₃-LaAlO₃ tie line from at least 4 mol% LaAlO₃ to pure LaAlO₃. With increasing LaAlO₃ content, the stabilized La_2/3TiO₃ structure changes from orthorombic via tetragonal to cubic.     

Suitable Glass-Ceramic Sealant for Planar Solid-Oxide Fuel Cells

Various glass-ceramics were prepared based on the BaO–Al₂O₃–B₂O₃–SiO₂ system with the addition of La₂O₃, ZrO₂, or NiO in an attempt to develop a suitable sealant for planar solid-oxide fuel cells operating at 800°C. To estimate the applicability of these glasses as suitable sealants, their thermal and chemical stabilities as well as the crystallization behavior and bonding characteristics of their parent glasses were investigated. The thermal properties and crystallization behavior of the parent glasses were dependent on the type of additive used, and the bonding characteristics were strongly influenced by the B₂O₃/SiO₂ value in the glass composition. Observation of microstructural change and chemical reaction at the glass-ceramic/electrolyte interface confirmed that the prepared glass-ceramics possessed long-term stability during heat treatment at the operation temperature for up to 1000 h.     

Electrical Resistance of Some Refractory Oxides and Their Mixtures in the Temperature Range 600° to 1500°C.

Measurements of electrical resistance in the composition systems Al₂O₃–SiO₂, SiO₂–TiO₂, Al₂O₃–Cr₂O₃, and MgO–NiO were made using, in general, dry-pressed disks about 3 cm. in diameter and 0.4 cm. thick and fired to 1500°C. In the Al₂O₃–SiO₂ series minimum resistance was shown by the samples containing 50% SiO₂, 50% Al₂O₃. The resistance of Al₂O₃ was increased by the addition of small amounts of Cr₂O₃. The same effect was observed in the higher temperature range with small additions of NiO to MgO. In other instances the addition of the relatively inert SiO₂, Al₂O₃, and MgO to the semiconductors TiO₂, Cr₂O₃, and NiO resulted in a dilution effect. The resistance of Cr₂O₃ was decreased by the addition of a slight amount of MgO.     

Acicular Mullite Crystals in Vitrified Kaolin

The microstructure of vitrified kaolin ceramic tapes has been studied via scanning and transmission electron microscopy (SEM and TEM). The sintered samples contained crystalline phase of predominantly stoichiometric mullite (3Al₂O₃·2SiO₂), which consisted of high aspect ratio, acicular crystals that are often referred to as secondary mullite. These crystals were interlocked and embedded in an aluminosilicate glass matrix of inhomogeneous composition. The glass matrix contained an average of ∼3.63 wt% K as determined by energy-dispersive X-ray analysis (EDS), whose composition could be approximated to 5Al₂O₃·16SiO₂·0.1MgO·0.3K₂O·0.15TiO₂·0.12Fe₂O₃. The acicular crystals have approximately the stoichiometric composition of Al₂O₃:SiO₂= 3:2. They have grown along a specific crystallographic orientation along the [001] axis. The crystal growth front exhibited facetting on the {110) planes with microfacetting on both the {100) and {010) planes.