Orientation Relationships of Reactively Grown Ba6Ti17O40 and Ba2TiSi2O8 on BaTiO3 (001) Determined by X-ray Diffractometry

Fresnoite grows at 700° and 800°C, and Ba₆Ti₇O₄₀ grows at 1200°C with definite orientations, which are determined by X-ray diffraction pole figure analysis. Partially textured fresnoite is formed at higher temperatures. The SiO₂ films react with the BaTiO₃ crystals, forming the phases Ba₂TiSi₂O₈ (fresnoite) and Ba₆Ti₁₇O₄₀. At 700° and 800°C, both phases grow with definite orientations, which are determined by X-ray diffraction pole figure analysis. Partially textured polycrystalline phases are formed at higher temperatures.     

Thermal Analysis of Magnesite at CO2 Pressures up to Six Atmospheres

The literature contains contradictory statements that the decomposition of magnesite is and is not affected by the pressure of CO₂ during the decomposition reaction. By means of the new variable-pressure differential thermal analysis technique, samples of Washington and Nevada magnesites were run at CO₂ pressures over the range 0.001 to 5000 mm. Hg. At 0.001 mm. Hg the endothermic loop starts at approximately 350°C., at 500° C. for 1 atmosphere of CO₂, and at 612°C. under 5000 mm. Hg pressure of CO₂. The results permit straightforward analysis of the mechanics of decomposition and comply with the Clausius-Clapeyron and Van't Hoff equations at CO₂ pressures above 250 mm. Hg.     

Low-Temperature Synthesis Route to MgNb2O6

A solution-derived precursor may be calcined at temperatures >500°C to yield MgNb₂O₆. Calcining temperatures 800°C result in the familiar, cation-ordered columbite structure type. Calcining temperatures <800°C result in a previously unobserved, cation-disordered α-PbO₂ structure type. The low-temperature form of MgNb₂O₆ is a more reactive material than is obtained by conventional solid-state reaction as evidenced by its small particle size and its ability to react with PbO to form lead magnesium niobate at lower temperatures.     

Preparation of PbZrO3–PbTiO3 Ferroelectric Thin Films by the Sol–Gel Process

Ferroelectric films, PbZr _x Ti_{1− x} O₃ ( x = 0 to 0.6), have been prepared from corresponding metal alkoxides partially stabilized with acetylacetone through the sol-gel process. The films dip-coated in an ambient atmosphere were heat-treated at 400°C for decomposition of residual organics and then at temperatures between 500° and 700°C for crystallization of the films. The perovskite phase precipitated at temperatures above 560°C, accompanied by an increase in dielectric constant. The dielectric constant of the films, which was comparable with that of sintered bodies, showed a maximum (∼620) at around x = 0.52 in PbZr _x Ti_{1− x} O₃. These films showed D – E hysteresis, with slightly higher values of coercive field, compared with those of sintered bodies.     

Preparation of an Alkali-Element-Doped CeO2-Sm2O3 System and Its Operation Properties as the Electrolyte in Planar Solid Oxide Fuel Cells

The ionic conductivity of the ceria-samaria (CeO₂-Sm₂O₃) system is higher than that of yttria-stabilized zirconia and other CeO₂-based oxides. In this study, a small amount of alkali-element-doped CeO₂-Sm₂O₃ solid solution was prepared. This solid solution was characterized by measuring the powder density and the chemical composition. Moreover, its electrochemical properties were investigated in the temperature range from 700° to 1000°C. It was found that a small amount of alkali-element-doped CeO₂ solid solution enhanced the ionic conductivity. The power density of an oxygen-hydrogen fuel cell for alkali-element-doped CeO₂-Sm₂O₃ ceramics exhibited high values at low temperatures such as 700° to 800°C. It is concluded that the improved fuel cell performance can be attributed to the high stability of this composition in the fuel atmosphere.     

PbTiO3-PbO-B2O3 Glass-Ceramics by a Sol-Gel Process

PbTiO₃ (PT)-PbO-B₂O₃ glass-ceramics were produced by a sol-gel process. Achievement of high PT content at levels unattainable by conventional glass-ceramics preparation methods was semiquantitatively shown. PT content was similar to the designed PT volume fraction and seemed rather unaffected by the composition of the glassforming component at a calcination temperature of 700°C. A higher ratio of PbO to B₂O₃ in the glassforming component resulted in a low PT crystallization temperature, <500°C. PT crystals 1-2 μm in size were obtained at calcination temperatures >600°C.     

Metal Organic Resin Derived Barium Titanate: I, Formation of Barium Titanium Oxycarbonate Intermediate

Crystallization of BaTiO₃ from an X-ray amorphous, metal organic precursor was investigated by comparing samples heated in O₂, air, argon, and CO₂. It is evident that an intermediate barium titanium oxycarbonate phase forms between 500° and 620°C and that BaTiO₃ forms directly by the endothermic decomposition of this phase between 635° and 700°C. From thermodynamic calculations, thermal analysis, X-ray diffraction, and Raman spectroscopy, it is concluded that the intermediate oxycarbonate is a highly disordered, metastable, and weakly crystalline phase with a stoichiometry close to Ba₂Ti₂O₅CO₃.     

Solid-State Diffusive Amorphization in TiO2/ZrO2 Bilayers

Thin films of crystalline TiO₂ were deposited on self-assembled organic monolayers from aqueous TiCl₄ solutions at 80°C; partially crystalline ZrO₂ films were deposited on top of the TiO₂ layers from Zr(SO₄)₂ solutions at 70°C. In the absence of a ZrO₂ film, the TiO₂ films had the anatase structure and underwent grain coarsening on annealing at temperatures up to 800°C; in the absence of a TiO₂ film, the ZrO₂ films crystallized to the tetragonal polymorph at 500°C. However, the TiO₂ and ZrO₂ bilayers underwent solid-state diffusive amorphization at 500°C, and ZrTiO₄ crystallization could be observed only at temperatures of 550°C or higher. This result implies that metastable amorphous ZrTiO₄ is energetically favorable compared to two-phase mixtures of crystalline TiO₂ and ZrO₂, but that crystallization of ZrTiO₄ involves a high activation barrier.     

Reactive Ceria Nanopowders via Carbonate Precipitation

Nanocrystalline CeO₂ powders have been successfully synthesized via a carbonate precipitation method, using ammonium carbonate (AC) as the precipitant and cerium nitrate hexahydrate as the cerium source. The AC/Ce³⁺ molar ratio ( R ) affects significantly precursor properties, and spherical nanoparticles can be produced only in a narrow range of 2 < R ≤ 3. The precursor, having an approximate composition of Ce(OH)CO₃·2.5H₂O, decomposes to CeO₂ at temperatures ≥300°C. The CeO₂ powder calcined at 700°C exhibits high reactivity and can be densified to >99% of theoretical at 1000°C.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.     

High-Temperature Phase Relations in Selected MnO-CrOx-Containing Systems

Phase relations in the pseudobinary MnO-CrO _x system were studied by the reaction of the individual oxides in the temperature range 1400°-1750°C under a reducing atmosphere with a CO:CO₂ volume ratio of 4.8, yielding oxygen partial pressures in the range 10^-9.98-10^-6.97 atm. In the pseudoternary MnO-CrO _x -containing systems that constitute the pseudoquaternary MnO-CrO _x -CaO-SiO₂ system, phase relations were determined only at 1500°C under an oxygen partial pressure of 10^−8.99 atm. Characteristic of these MnO-CrO _x -containing systems was the dominance of the (Mn,Cr)₃O₄ spinel phase.     

Characteristics of Si3N4-SiO2-Ce2O3 Compositions Sintered in High-pressure Nitrogen

Full-density Si₃N₄-SiO₂-Ce₂O₃ compositions were prepared by sintering with 2.5 MPa nitrogen pressure at temperatures of 1900° and 2090°C. Room-temperature flexural strengths near 700 MPa for sintered material compared favorably with the strength of hot-pressed material. At 1370°C, where flexural strengths as high as 363 MPa were obtained, it was observed that the coarsest structure was the strongest and the finest structure was the weakest. One of the compositions tested, Si₃N₄-8.7 wt% SiO₂-8.3 wt%-Ce₂O₃, was found to have excellent 200-h oxidation resistance at 700°, 1000°, and 1370°C, without incidence of 700° to 1000°C phase instability and cracking.     

Sol–Gel Route to Nanocrystalline Lithium Metasilicate Particles

Crystalline lithium metasilicate (Li₂SiO₃) nanoparticles have been synthesized using a sol–gel process with tetraethylorthosilicate and lithium ethoxide as precursors. The particle size examined by using transmission electron microscopy and BET-specific surface area techniques is in the range 5–50 nm, depending on the temperature at which the material is calcined. The crystalline Li₂SiO₃ forms at ambient temperature (∼40°C), and it remains in this phase after calcination at temperatures up to 850°C. The BET-specific surface area is ∼110 m²/g for material calcined at temperatures below 500°C, decreasing to ∼29 and ∼0.7 m²/g following calcination at 700° and 850°C, respectively. Solid-state ²⁹Si NMR spectroscopy shows the presence of only Q ² structural units in the material. The lithium metasilicate is further characterized using differential scanning calorimetry and thermogravimetric analysis, and Fourier transform infrared spectroscopy.     

Melting Reactions of Soda-Lime-Silicate Glasses Containing Sodium Sulfate

Various Na₂SO₄-Na₂CO₃-CaCO₃-SiO₂ combinations were studied by differential thermal analysis to elucidute the role of Na₂SO₄ in soda-lime-silica glassmelting reactions. It was found that Na₂SO₄ encourages the formation of wollastonite at 850° to 900°C. The solid-state reaction of Na₂Ca(CO₃)₂ occurs very readily at temperatures in the vicinity of 400°C. The Na₂Ca(CO₃)₂ must therefore be considered a major constituent in glass batches containing both soda ash and limestone .     

Stability of Molybdenum Disilicide in Combustion Gak Environments

The stability of MoSi₂ in combustion gas at 1370° and 1600°C was evaluated using SOLGASMIX-PV thermodynamic modeling, periodic weight measurements, and characterization via XRD, SEM, EDS, and image analysis. Passive oxidation occurred at both temperatures. During an initial stage of exposure, specimen surfaces oxidized to form MoO_3(g) and amorphous SiO₂ via reduction of CO₂ and H₂O. After a short time (<6.5 min at 1370°C, <1 min at 1600°C), the oxidation mechanism switched; Mo₅Si₃ and amorphous SiO₂ formed as oxidation products. The first mechanism esulted in the formation of 46.1 vol% at 1370°C and 42.6 vol% at 1600°C of the amorphous silica surface coating. The attainment of a near-terminal weight gain implied silica formation was limited by H₂O and CO₂ diffusion through the silica coating.     

Formation and Stability of Ferroelectric BaTi2O5

BaTi₂O₅ (BT₂) is thermodynamically stable over a very narrow temperature range between 1220° and 1230°C: a modification to the BaO–TiO₂ phase diagram is proposed. This thermodynamic stability was shown by constructing a time–temperature transformation diagram for the decomposition of BT₂. Once formed, BT₂ appears to be stable indefinitely at 1220°–1230°C; at higher temperatures, the decomposition rate increases with temperature; at lower temperatures, the decomposition rate increases with decreasing temperature and passes through a maximum at ∼1200°C; below ∼1150°C, BT₂ has long-lived kinetic stability. Kinetic considerations show a nucleation and growth mechanism for decomposition, with a nucleation induction period that is very temperature dependent. BT₂ can be prepared by various routes, including solid-state reaction of oxides below ∼1100°C; because it is metastable at all temperatures other than 1220°–1230°C, its formation is an example of Ostwald's rule of successive reactions. Discrepancies in the literature concerning the reported stability range of BT₂ can be explained by the complex dependence on temperature and time of both its formation and decomposition, for both of which, the nucleation stage is rate limiting.     

Soft-Chemistry Synthesis, Characterization, and Stabilization of CGO/Al2O3/Pt Nanostructured Composite Powders

Soft-chemistry routes were used to synthesize Ce_0.9Gd_0.1O_1.95-based powders with attractive and stable structural, morphological, and textural properties. In the intermediate temperature range between 500° and 700°C, the average Gd-doped CeO₂ (CGO) crystallite size is in the range 9–22 nm and the specific surface area varies from 43.4 to 8 m²/g. Above 700°C, a phase separation occurs between ceria and gadolinium oxide. Addition of alumina was found to be useful in stabilizing the CGO nanocrystallites at a high temperature and to avoid phase separation. A homogeneous dispersion of Pt nanoparticles (<10 nm at 1000°C) in the CGO materials was found to be possible by post-impregnation, although direct insertion of the Pt precursors during the synthesis led to aggregated particles, with less potential for catalytic applications.     

SiO2/Fe2O3 Mesoporous Composite Prepared With an Activated Carbon Template in Supercritical Carbon Dioxide

SiO₂/Fe₂O₃ mesoporous composites have been prepared with a nanoscale casting process using an activated carbon (AC) template in supercritical carbon dioxide (SC CO₂). The composite precursor and acetone solvent (for Fe₂O₃ precursor) were dissolved in SC CO₂, and then coated on the AC in the desired supercritical condition. After removal of the AC template by calcinations in air at 600°C, SiO₂/Fe₂O₃ mesoporous composite were obtained. Temperature, pressure, and composite precursor ratio effects were studied. Scanning electron microscopy result shows that the porous structure of AC template had been well replicated by the composite product. Transmission electron micrograph indicates that nano iron oxides were well dispersed in the composite product.     

Binary Titania-Silica Glasses Containing 10 to 20 Wt% TiO2

A series of glasses in the TiO₂-SiO₂ system was prepared by the flame hydrolysis boule process. Clear glasses containing as much as 16.5 wt% TiO₂ were obtained. More TiO₂ caused opacity due to phase separation and anatase/rutile crystallization during glass boule formation. Glasses in the 12 to ∼17 wt% TiO₂ range were metastable and showed structural rearrangements on heat treatment at temperatures as low as 750CEC (∼200° below the annealing point). These changes were accompanied by large changes in thermal expansion. Thermal treatment can be designed to produce almost any desired expansion between α_-200+700=−5 × 10^-7/°C and +10 × 10^-7/°C. Zero expansion between 0 and 550°C was obtained. Evidence that these changes are due to phase separation and anatase formation is presented. Viscosity data in the glass transition range, refractive index, and density are also presented.     

Preparation and Characterization of Chemically Vapor Deposited ZrO2 Coating on Nickel and Ceramic Fiber Substrates

Monoclinic ZrO₂ was deposited on several metallic and ceramic substrates by reacting ZrCl₄, CO₂, and H₂ at temperatures of 800° to 1050°C. Ni substrates reacted significantly in the ZrO₂ coating environment since the coating was porous and contained a considerable amount of Ni. In contrast, the coating deposited on SiC and aluminoborosilicate fibers was highly crystalline, faceted, and dense without any apparent interaction with the substrate materials.