Growth of β-Alumina (Na2O · 11Al2O3) Single Crystals by the Flux Method

The crystal-growth process and growth conditions of β-alumina (Na₂O · Al₂O₃) were investigated using the Na₂B₄O₇-Na₃AlF₆ flux method. β-Alumina (electric fusion brick) was used as both nutrient and seed. Weight loss of the flux varied widely for various runs: ≅ 10 wt% of flux evaporated at 100 h, ≅ 17 wt% at 150 h, and 43 wt% at 600 h. When β-alumina crystal was grown, only 20 wt% Na₂B₄O₇ was added to the Na₃AlF₆ flux. The linear growth rates of the β-alumina single crystal grown by an Na₃AlF₆-20 wt% Na₂B₄O₇ flux method at 1040°C and Δ t = 18°C were ≅ 1.0 × 10⁻³ mm/h ( a face) and ≅0.3 × 10⁻³ mm/h ( c face). The β-alumina single crystals grown were bounded by only c [001] and a [100] and were colorless and transparent.     

Growth of α-Al2O3 Crystals by Na2O Evaporation

A technique for growing α-Al₂O₃ crystals is described in which Na₂O·11Al₂O₃ is dissolved in a liquid of composition Na₂O·4TiO₂·3Al₂O₃. Alpha Al₂O₃ is precipitated as Na₂O evaporates from the system; Na₂O·11Al₂O₃ serves as a source of Al₂O₃, and Na₂O in the liquid. The content of solids in the mixture is always such that it does not melt completely. The size of the α-Al₂O₃ crystals grown is related to the Na₂O content of the composition. Crystals as large as 4000 by 3000 μm in the α-axis direction and 500 μm in the c -axis direction have been grown.     

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.     

Identification of α-Al2O3 Precipitates in Rutile Single Crystals

After high-temperature reaction between Al₂O₃ and TiO₂ crystals, precipitates found in rutile were characterized by electron microprobe and X-ray diffraction methods and by optical and electron microscopy. The precipitates were identified as α-Al₂O₄. Geometric and crystallographic orientation relations with the TiO₂ matrix constitute a reverse case of rutile precipitation in star sapphire .     

Stabilization of β-Bi2O3 by Sb2O3 Doping

The metastable β form of bismuth sesquioxide was obtained by doping antimony oxide. The solubility of antimony was 4 to 10 at. %in β specimens, where more than 75% of the antimony atoms were valenced at 5+.     

Leaching of Glasses with Molar Composition 20Na2O · 10RO ·x Al2O3· (70-x)SiO2

Sodium depth profiles were determined in water-leached glass samples with molar composition 20Na₂O · 10RO · x Al₂O₃· (70 - x)SiO₂ (RO = CaO, MgO, and ZnO) using secondary ion mass spectrometry. The leaching of sodium ions decreases with increasing Al₂O₃ content in all three glass systems. For x = 0 the leaching is hardly affected by the nature of the divalent cation. For x = 5 and 10 the corrosion resistance is highest for the glass containing ZnO, and for the glasses containing ZnO and MgO, respectively. These glasses correspond to those with the smallest fraction of NBOs. From all these results it is concluded that the nonbridging oxygen atoms play an important role in promoting the leaching of a glass.     

Modification of αAI2O3 Platelet/ZrO2 Matrix Interface by Epitaxial Growth of β-AI2O3 on the α-AI2O3

An epitaxial β-alumina crystal growth method was used to modify α-AI₂O₃ platelet surfaces before inclusion as a reinforcing phase in partially stabilized zirconia (3Y-TZP). The as-grown surface phase was Na-β"-AI₂O₃. This was converted to Ca-β"-AI₂O₃ by ion exchange, as the latter is more temperature-stable at composite sintering temperatures. The conditions of formation, thermal stability, and chemical compatibility of these interfacial phases were examined. α-AI₂O₃ platelets with Ca-β"-AI₂O₃ film were incorporated into 3Y-TZP. The β"-AI₂O₃/ZrO₂ interface was found to promote platelet debonding and pullout, thus enhancing the α-AI₂O₃ platelet/crack interactions during the fracture process.     

Electrical Conduction in β-Bi2O3 Doped with Sb2O3

Electrical conduction in tetragonal β-Bi₂O₃ doped with Sb₂O₃ was investigated by measuring electrical conductivity, ionic transference number, and Seebeck coefficient. The β-Bi₂O₃ doped with 1 to 10 mol% Sb₂O₃ was stable up to 600°C and showed an oxygen ionic and electronic mixed conduction, where the electron conduction was predominant at low oxygen pressures. The oxygen-ion conductivity showed a maximum at 4 mol% Sb₂O₃, whereas the activation energy for the ionic conduction remained unchanged for 4 to 10 mol% Sb₂O₃-doped specimens. These results were interpreted in terms of the oxygen vacancy concentration and the distortion of the tetragonal structure. The electron conductivity and its oxygen pressure dependence decreased with increasing Sb₂O₃ content. The fact that Sb⁵⁺ is partially reduced by excess electrons in heavily doped β specimens at low oxygen pressures is explained.     

Defects and Charge Transport in β-Ta2O5: II, Analysis of the Conductivity of Nb2O5-doped β-Ta2O5

The model proposed to explain the defect behavior of nominally pure β-Ta₂O₅ was extended to the case of defect equilibria and charge transport in β-Ta₂O₅ doped with a multivalent cation, i.e., Nb₂O₅-doped P-Ta₂O₅. This case is of practical interest in the electronics industry, where Nb₂O₅, is a dominant impurity in capacitor-grade β-Ta₂O₅.     

Phase Formation in the System Na2O · Al2O3-CaO · A12O3-Al2O3 at 1200°C in Air

Phase relations in the system Na₂O_· Al₂O₃-CaO· Al₂O₃-Al₂O₃ at 1200°C in air were determined using the quenching method and high-temperature X-ray diffraction. The compound 2Na₂O · 3CaO · 5Al₂O₃, known from the literature, was reformulated as Na₂O · CaO · 2Al₂O₃. A new compound with the probable composition Na₂O · 3CaO · 8Al₂O₃ was found. Cell parameters of both compounds were determined. The compound Na₂O · CaO-2Al₂O₃ is tetragonal with a = 1.04348(24) and c = 0.72539(31) nm; it forms solid solutions with Na₂O · Al₂O₃ up to 38 mol% Na₂O at 1200°C. The compound Na₂O · 3CaO · 8Al₂O₃ is hexagonal with) a = 0.98436(4) and c = 0.69415(4) nm. The compound CaO · 6Al₂O₃ is not initially formed from oxide components at 1200°C but behaves as an equilibrium phase when it is formed separately at higher temperatures. The very slow transformation kinetics between β and β "-Al₂O₃ make it very difficult to determine equilibrium phase relations in the high-Al₂O₃ part of the diagram. Conclusions as to lifetime processes in high-pressure sodium discharge lamps can be drawn from the phase diagram.     

Differences in Surface Behavior of Alkali Ions in Li2O ·3SiO2 and Na2O · 3SiO2 Glasses

The molecular dynamics computer simulation technique was used to determine the short-time dynamics behavior and resultant structures of ions at the surface of Li₂0·3SiO₂ and Na₂O-3SiO₂ glasses. Room temperature and elevated temperatures were used. Results are compared with similar studies of the K₂O·3SiO₂ glass surface and with recent experimental ion-scattering-spectroscopy data. The simulations indicate that a localized surface rearrangement occurs within picoseconds after formation of the free surface, creating a surface excess of alkali in the Na (and K) case, but not in the Li case. Elevated temperatures, even for brief times, enhance the observed surface excess of Na and K. The results correspond to those obtained from the ion-scattering-spectroscopy studies.     

Characterization of Freeze-Dried Al2O3 and Fe2O3

Oxide crystallite formation and growth from freeze-dried sulfates were studied for the representative materials Al₂O₃ and Fe₂O₃. Transmission and scanning electron micrographs showed the formation and growth of chainlike aggregates of crystallites. Aggregation occurred as part of the nucleation and growth of the oxide, and discrete oxide particles were never present. Orientation of the chain aggregates was related to the ice structure formed during freezing. X-ray line broadening data showed that crystallite size is a function of the 1/5 to 1/7 power of time for isothermal treatments. A qualitative analysis of material transport favored the surface diffusion mechanism.     

Dissociation Pressures of Solid Solutions from Fe3O4 to 0.4Fe3O4·0.6CoFe2O4

The dissociation pressures of solid solutions from Fe₃O₄ to 0.4Fe₃O₄·0.6CoFe₂O₄ have been determined as a function of temperature. Within experimental error, solid solutions within this range are thermodynamically ideal.     

Thermodynamic Properties of Fe3O4-FeV2O4 and Fe3O4-FeCr2O4 Spinel Solid Solutions

Solid solutions of Fe304-FeV204 and Fe304-FeCr204 were prepared and equilibrated with Pt under controlled streams of CO/CO, gas mixtures at 1673 K. The concentration of Fe in Pt was used to determine the activity of Fe304 in the solid solutions. The activity of the second component was calculated by Gibbshhem integration. From these data, the Gibbs energy of mixing was derived for both systems. The experimental results and theoretical values which are determined from calculated cation distribution compare favorably in the case of vanadite solid solutions but not in the case of chromite solid solutions. The difference is attributed to a heat term arising from lattice distortion due to cation size difference. The positive heat of mixing will give rise to a miscibility gap in the system Fe304-FeCr204 at lower temperatures.     

In Situ Formation of Hexaferrite Magnets within a 3Y-TZP Matrix: La2O3–ZnO–Fe2O3 and BaO–Fe2O3 Systems

The in situ formation of magnetoplumbite-type (M-type) hexaferrites within a 3Y-TZP matrix was examined for the La₂O₃–ZnO–Fe₂O₃ and BaO–Fe₂O₃ systems. The formation of barium hexaferrite (Ba-M) was rapid enough at a temperature of 1300°C for 2 h to result in a uniform dispersion of fine Ba-M particles in a tetragonal zirconia polycrystal (TZP) matrix. However, the formation of lanthanum-substituted hexaferrite (La-M) was rather sluggish, despite the existence of a charge-compensating divalent oxide. The 3Y-TZP/20-wt%-BaFe₁₂O₁₉ in situ composite possessed good magnetic properties, as well as moderately good mechanical properties.     

Compressive Creep of Al2O3 Single Crystals

Aluminum oxide single crystals deformed by dislocation glide and deformation twinning during compressive creep at 1400° to 1700°C. The activation energy for basal slip was a function of the applied stress and agreed with activation energies previously measured by observation of yielding phenomena. The overcoming of a large Peierls-Nabarro stress is the most probable rate-controlling mechanism. Rhombohedral twinning, a significant deformation mode in creep, depends on surface damage for nucleation. The activation energy for rhombohedral twin growth, a function of the applied stress, is substantially lower than that for basal slip. When basal slip and rhombohedral twinning occur concurrently, creep by basal slip results, but the presence of twins can substantially reduce the creep rate.