Effect of Titania and Lithia Doping on the Boundary Migration of Alumina under an Electric Field

Boundary migration under an electric field was investigated for pure, TiO₂-doped, and Li₂O-doped Al₂O₃ specimens. Boundary migration rates in TiO₂-doped and Li₂O-doped Al₂O₃ specimens were much faster compared with that of pure Al₂O₃. In all specimens, the migration rate was observed to depend on the applied bias direction. Compared with pure Al₂O₃, the dependence of boundary migration on bias direction became more pronounced in TiO₂-doped Al₂O₃ but less pronounced in Li₂O-doped Al₂O₃. The results were explained in terms of the variation of grain sizes, mobility, and electrostatic potential of boundaries because of doping.     

Studies in Lithium Oxide Systems: IX, Li2o-Al2O3-TiO2

Compatible phases in the system Li₂O-Al₂O₃-TiO₂ at various temperature levels were determined mainly by solid-state reactions for the portion of the ternary system bounded by Li₂O Al₂O₂, Li₂O.TiO₂, Al₂O, and TiO₂. The existence of a ternary compound, Li₂O.Al₂O₃.4TiO₂, and nine joins was established. The ternary compound has a lower limit of stability at 1090°± 15°C. and dissociates and recombines rapidly at 1380°± 15°C.     

Some Roles of MgO and TiO2 in Densification of a Sinterable Alumina

Sinterability of undoped, MgO-doped, and TiO₂-doped Al₂O₃ has been examined by applying reported sintering equations. The order of sinterability was MgO-doped ∼ undoped≪ TiO₂-doped Al₂O₃ in the initial and intermediate stages of sintering, but a relative sintered density at 1600°C for 1 h occurred in the order undoped < TiO₂-doped < MgO-doped AI₂O₃. The dispersion of thermal grooving angles increased in the order MgO-doped < undoped < TiO₂-doped Al₂O₃, The change of sinterability by the dopants is explained in terms of mobility of mass transfer estimated from a densification rate in the initial- and intermediate-stage sintering and of dispersed driving forces of densification and grain growth qualitatively evaluated from the width of the dispersion of thermal grooving angles.     

Direct-Current Field Dependence of Dielectric Properties in Alumina-Doped Barium Strontium Titanate

The dielectric properties of (Ba_0.6Sr_0.4)TiO₃ and Al₂O₃-doped (Ba_0.6Sr_0.4)TiO₃ have been characterized. The grain size of the specimen is maximum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃. The density and the real part of the relative dielectric constant each decrease as the Al₂O₃ content increases. The loss factor is minimum for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 2 wt% Al₂O₃. The dielectric constant of the specimens decreases as the applied dc field increases. The influence of the dc field on the loss factor is much less than that on the dielectric constant. The tunability is ∼24% for (Ba_0.6Sr_0.4)TiO₃ that has been doped with 1 wt% Al₂O₃.     

Evidence of Bilevel Solubility in the Bimodal Microstructure of TiO2-Doped Alumina

A phenomenon of bilevel solubility was observed in a TiO₂-doped (2.0 wt%) alumina with bimodal microstructure sintered in N₂. Surface contributions to dopant signals in individual grains were identified and removed, using a spatially resolved energy dispersive spectroscopy analysis. Two levels of solubility, 1.005 ± 0.166 and 0.504 ± 0.082 mol% of TiO₂ in Al₂O₃, were obtained for anisotropic and equiaxed grains, respectively. No grain size dependence of solubility was found, but segregation of SiO₂ to boundaries with the anisotropic grains was observed. This phenomenon was explained by the incorporation of Ti³⁺ into the Al₂O₃ lattice during the abnormal grain growth caused by SiO₂ liquid under a reducing atmosphere.     

Ionically Conducting Composite Membranes from the Li2O–Al2O3–TiO2–P2O5 Glass–Ceramic

This paper reports processing of lithium ion-conducting, composite membranes comprised of 14Li₂O·9Al₂O₃·38 TiO₂·39P₂O₅ glass–ceramic and polyethylene. The processing involved tape casting of 14Li₂O·9Al₂O₃·38TiO₂·39P₂O₅ glass powder with organic additives into tapes, subjecting the green tape to binder burnout and thermal soaking in the temperature range of 950°–1100°C, and finally infiltrating the porous tape with polyethylene solution. The ionic conductivity and microstructure of 150–350 μm thick membranes were characterized and are discussed in this paper. The crystallites of the glass–ceramic show liquid-like conductivity at ambient temperature, whereas the grain boundary conductivity is lower by a factor of five. The lower grain boundary conductivity is explained on the basis of crystallographic mismatch and the existence of AlPO₄ at the grain boundary. The polyethylene infiltration in the porous membrane improved mechanical resilience with a minor adverse effect on conductivity.     

Fabrication and Microstructure Characterization of Continuous Porous TiO2/Al2O3 Composite Membrane

Using a multipass extrusion process, continuous porous Al₂O₃ body (∼41% porosity) was produced and used as a substrate to fabricate continuous porous TiO₂/Al₂O₃ composite membrane. The diameter of the continuous pores of the porous Al₂O₃ body was about 150 μm. The TiO₂ nanopowders dip coated on the continuous pore-surface Al₂O₃ body existed as rutile and anatase phases after calcination at 520°C in air. However, after aging of the fabricated continuous porous TiO₂/Al₂O₃ composite membrane in 20% NaOH at 60°C for 24 h, a large number of TiO₂ fibers frequently observed on the pore surface. The diameter of the TiO₂ fibers was about 150 nm having a high specific surface area. However, after 48-h aging period, the diameter of the TiO₂ fibers increased, which was about 3 μm. Most of the TiO₂ fibers had polycrystalline structure having nanosized rutile and anatase crystals of about 20 nm.     

Reduction of Eu3+ to Eu2+ in Aluminoborosilicate Glasses Prepared in Air

Eu₂O₃-doped aluminoborosilicate glasses were prepared in air at high temperature. Luminescence measurements were used to investigate a valence change from Eu³⁺ to Eu²⁺ ions in the aluminoborosilicate glasses. The results showed that the doped Eu³⁺ ions were partially reduced to Eu²⁺ in the Eu₂O₃:RO–Al₂O₃–B₂O₃–SiO₂ (RO=CaO, SrO, BaO, Li₂O) glasses, but not in the Eu₂O₃:RO–Al₂O₃–B₂O₃–SiO₂ (RO=Na₂O, K₂O) glasses. The changes of Eu reduction with different RO components were discussed with the variation of optical basicity of RO and with different valency of R cations. The effects of co-doping BaO and ZnO in aluminoborosilicate glasses on Eu reduction were also investigated and discussed.     

Densification and Thermal Conductivity of AIN Doped with Y2O3, CaO, and Li2O

Small amounts of Li₂O result in sintering in the AIN-Y₂O₃-CaO and AIN-CaO systems at firing temperatures <1600°C. The effect is ascribed to reduction of the liquidus temperature. Furthermore, Li₂O is removed by volatization at temperatures from 1300° to 1600°C, and its content decreases several ppm from the initial 0.3 wt%. Li₂O-doped AIN specimens containing Y₂O₃ and CaO additives are well densified by firing at 1600°C for 6 h, and their thermal conductivity is 135 W^.m^−1.K⁻¹.The effect of Li₂O addition on sintering and thermal conductivity also is discussed through thermo-dynamic considerations.     

Studies in Lithium Oxide Systems: II, Li2O Al2O3–Al2 O 3

Solid-state reactions between Li₂O and Al₂ O₃ were studied in the region between Li₂O.Al₂ O ₃ and Al₂ O ₃. The compound Li₂ O Al₂ O ₃ melts at 1610°± 15°C. and undergoes a rapid reversible inversion between 1200° and 1300°C. Vaporization of Li₂ O from compositions in the system proceeds at an appreciable rate at 1400°C, as shown by fluorescence. Lithium spinel, Li₂ O -5Al₂O₃, was the only other compound observed. The effect of Li₂ O on the sintering of alumina was investigated.     

Microstructure and Mechanical Properties of Porous Alumina Ceramics Fabricated by the Decomposition of Aluminum Hydroxide

The mechanical properties of Al₂O₃-based porous ceramics fabricated from pure Al₂O₃ powder and the mixtures with Al(OH)₃ were investigated. The fracture strength of the porous Al₂O₃ specimens sintered from the mixture was substantially higher than that of the pure Al₂O₃ sintered specimens because of strong grain bonding that resulted from the fine Al₂O₃ grains produced by the decomposition of Al(OH)₃. However, the elastic modulus of the porous Al₂O₃ specimens did not increase with the incorporation of Al(OH)₃, so that the strain to failure of the porous Al₂O₃ ceramics increased considerably, especially in the specimens with high porosity, because of the unique pore structures related to the large original Al(OH)₃ particles. Fracture toughness also increased with the addition of Al(OH)₃ in the specimens with higher porosity. However, fracture toughness did not improve in the specimens with lower porosity because of the fracture-mode transition from intergranular, at higher porosity, to transgranular, at lower porosity.     

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.     

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.     

Aluminum Titanate Formation by Solid-State Reaction of Coarse Al2O3 and TiO2 Powders

Reaction kinetics in a coarse equimolar powder mixture were slow enough to allow for the different stages to be identified, notably in the lower and higher temperature ranges, respectively. In the former ( T ≤ 1600 K), Al₂TiO₅ nucleation was hindered by the strain energy contribution to the overall driving force. The setting up of metastable layer sequences Al₂TiO₅/TiO₂/Al₂O₃ was found to occur generally during subsequent growth. The high Al mobility in the TiO₂ provided a rapid aluminum transport from the metastable Al₂O₃/TiO₂ interface to the TiO₂/Al₂TiO₅ front. At temperatures above ∼1700 K the Al₂O₃/TiO₂ interface was very rapidly sealed off by Al₂TiO₅ formation. Reactant transport across the Al₂TiO₅ was slow because of the low mobilities in the product phase. Therefore, much lower product growth velocities were observed at higher temperatures than at lower temperatures.     

Effect of Electric Field on the Migration of Grain Boundaries in Alumina

The effect of an external electric field on the grain-boundary migration in Al₂O₃ ceramics has been investigated. The boundary migration is dependent on the direction and magnitude of the applied bias, and the observed boundary migration behavior is attributed to the presence of an electrostatic potential that inherently forms at the grain boundaries of Al₂O₃ ceramics. The results give experimental evidence that the boundary phenomena in oxide ceramics are related to the grain-boundary potential.     

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.     

Preparation and Sintering of Monosized Al2O3-TiO2 Composite Powder

An unagglomerated, monosized Al₂O₃TiO₂ composite powder was prepared by the stepwise hydrolysis of titanium alkoxide in an Al₂O₃ dispersion. Particle size was controlled by selecting the particle size of the starting Al₂O₃ powder; TiO₂ content was determined by the amount of alkoxide hydrolyzed. A composite-powder compact containing 50 mol% TiO₂, when fired at 1350°C for 30 min, showed nearly theoretical density with aluminum titanate phase formation.     

Mullite Transformation Kinetics in P2O5-, TiO2-, and B2O3-Doped Aluminosilicate Gels

Mullite transformation kinetics of sol-gel-derived diphasic mullite gels doped with P₂O₅, TiO₂, and B₂O₃ were studied using quantitative X-ray diffraction and differential thermal analysis (DTA). The mullite transformation temperature initially increased with P₂O₅ doping because of phase separation and formation of α-alumina and cristobalite. In TiO₂-doped samples, the mullite transformation temperature decreased with TiO₂ doping, and the transformation rate increased with decreasing TiO₂ particle size. Kinetic studies showed that titania reduced the activation energy for both nucleation and growth relative to pure diphasic mullite gels by lowering the glass viscosity and/or enhancing the solid-state mass transport through lattice defects. B₂O₃ doping decreased the mullite transformation temperature and lowered the activation energy for both nucleation and growth but especially affected the mullite nucleation process, as indicated by the much smaller grain size.     

Acoustic Characterization of Silica Glasses

Acoustic characterization of doped silica glasses with a GeO₂, P₂O₅, F, TiO₂, Al₂O₃, or B₂O₃ dopant having different concentrations is presented. Quantitative measurements were performed with a 225-MHz line-focus-beam scanning acoustic microscope. The acoustic velocity variation due to different dopant concentrations is given. It has been found that the Al₂O₃ dopant increases, but the other dopants decrease, the acoustic velocity as compared with that of the pure fused silica. We have also found that the fractional change in acoustic velocity is greater than that in refractive index for a given dopant concentration.     

Formation and Transformation of TiO2 (Anatase) Solid Solution in the System TiO2—Al2O3

In the system TiO₂—Al₂O₃, TiO₂ (anatase, tetragonal) solid solutions crystallize at low temperatures (with up to ∼ 22 mol% Al₂O₃) from amorphous materials prepared by the simultaneous hydrolysis of titanium and aluminum alkoxides. The lattice parameter a is relatively constant regardless of composition, whereas parameter c decreases linearly with increasing Al₂O₃. At higher temperatures, anatase solid solutions transform into TiO₂ (rutile) with the formation of α-Al₂O₃. Powder characterization is studied. Pure anatase crystallizes at 220° to 360°C, and the anatase-to-rutile phase transformation occurs at 770° to 850°C.