Dense Alumina–Zirconia Coatings Using the Solution Precursor Plasma Spray Process

For the first time, dense coatings have been made by the solution precursor plasma spray (SPPS) process. The conditions are described for the deposition of dense Al₂O₃–40 wt% 7YSZ (yttria-stabilized zirconia) coatings; the coatings are characterized and their thermal stability is evaluated. X-ray diffraction analysis shows that the as-sprayed coating is composed of α-Al₂O₃ and tetragonal ZrO₂ phases with grain sizes of 72 and 56 nm, respectively. The as-sprayed coating has a 95.6% density and consists of ultrafine splats (1–5 μm) and unmelted spherical particles (<0.5 μm). The lamellar structure, typical of conventional plasma-sprayed coatings, is absent at the same scale in the SPPS coating. The formation of a dense Al₂O₃–40 wt% 7YSZ coating is favored by the lower melting point of the eutectic composition, and resultant superheating of the molten particles. Phase and microstructural thermal stabilities were investigated by heat treatment of the as-sprayed coating at temperatures of 1000°–1500°C. No phase transformation occurs, and the grain size is still in the nanometer range after the 1500°C exposure for 2 h. The coating hardness increases from 11.8 GPa in the as-coated condition to 15.8 GPa following 1500°C exposure due to a decrease in coating porosity.     

Dy:YAG Phosphor Coating Using the Solution Precursor Plasma Spray Process

Dy:YAG phosphor coatings were deposited using the solution precursor plasma spray process. The phase composition, microstructure, and photoluminescent properties of the as-deposited coatings were investigated. X-ray diffraction analysis confirmed that the coating is mainly composed of the YAG phase with a small amount of an intermediate YAP phase. Scanning electron microscopy micrograph revealed that the as-sprayed coating has columnar structures with a thickness of ∼60 μm. The measurement of photoluminescent properties indicated that the phosphor coating exhibits two predominant emission regions: a blue region (470–500 nm) and a yellow region (560–600 nm), which are assigned to ⁴F_9/2–⁶H_15/2 and ⁴F_9/2–⁶H_13/2 transitions, respectively.     

Formation and Sintering of TiO2 (Anatase) Solid Solution in the System TiO2-SiO2

In the TiO₂-SiO₂ system, anatase solid solutions (ss) containing up to similar/congruent ∼15 mol% SiO₂ are formed in the as-prepared state by the hydrazine method. The lattice parameters a and c decrease linearly from 0.3785 to 0.3776 nm and from 0.9514 to 0.9494 nm, respectively, with increased SiO₂ content. At high temperatures, the solid solutions by transformation decompose into rutile and amorphous SiO₂. The anatase(ss) powders have been characterized for particle size and surface area. They consist of very fine particles (7-25 nm). Surface areas at low temperatures are very high and do not drop below 60 m²/g at 1000°C. Nanostructured anatase(ss) ceramics, with greaterthan/equal to 99.5% of theoretical density and an average grain size of 72 nm, have been fabricated by hot isostatic pressing for 1 h at 850°C and 196 MPa. Their mechanical and electrical properties have been examined.     

Homogeneous Precipitation of TiO2 Ultrafine Powders from Aqueous TiOCl2 Solution

Crystalline TiO₂ powders were prepared by the homogeneous precipitation method simply by heating and stirring an aqueous TiOCl₂ solution with a Ti⁴⁺ concentration of 0.5 M at room temperature to 100°C under a pressure of 1 atm. TiO₂ precipitates with pure rutile phase having spherical shapes 200-400 nm in diameter formed between room temperature and 65°C, whereas TiO₂ precipitates with anatase phase started to form at temperatures >65°C. Precipitates with pure anatase phase having irregular shapes 2-5 µm in size formed at 100°C. Possibly because of the crystallization of an unstable intermediate product, TiO(OH)₂, to TiO₂ x H₂O during precipitation, crystalline and ultrafine TiO₂ precipitates were formed in aqueous TiOCl₂ solution without hydrolyzing directly to Ti(OH)₄. Also, formation of a stable TiO₂ rutile phase between room temperature and 65°C was likely to occur slowly under these conditions, although TiO₂ with rutile phase formed thermodynamically at higher temperatures.     

Solubility of TiO2 in ZrO2

The solubility of TiO₂ in tetragonal ZrO₂ is 13.8±0.3 mol% ui 1300°C, 14.9±0.2 mol% at 1400°C, and 16.1±0.2 mol% at 1500°C. These solid solutions transform to metastable monoclinic solid solutions without compositional change on cooling to room temperature.     

Nanostructure of TiO2 Nano-Coated SiO2 Particles

We characterized SiO₂–TiO₂ nano-hybrid particles, prepared using the sol–gel method, using high-resolution transmission microscopy. A few nanometer-ordered TiO₂ anatase crystallites could be observed on the monodispersed SiO₂ nanoparticle surface. The quantum size effect of the TiO₂ anatase crystallites is attributed to the blue shift of the absorption band. The rough surface of the SiO₂–TiO₂ nano-hybrid particles was derived from the developed growth planes of the TiO₂ anatase crystallites, grown from fully hydrolyzed Ti alkoxide that did not react with acetic acid during the crystallization process at 600°C thermal annealing.     

Solubility of TiO2 in BaTiO3

Scanning electron microscopy and electron probe micro-analysis were used to investigate the microstructure of both slow-cooled and quenched polycrystalline BaTiO₃ specimens with a small excess of TiO₂ (Ba/Ti=0.995 to 0.999) or of BaO (Ba/Ti=1.002 and 1.005). The electron micrographs of polished and etched TiO₂-excess BaTiOs samples, and of fracture surfaces of quenched samples, showed a second phase in the grain boundaries and triple-point regions, whereas no second phase was observed in samples having Ba/Ti=1.000. Microprobe analysis of the second phase gave compositions near that of the reported adjacent phase of higher TiO₂ content, Ba₆Ti₁₇O₄₀. The results indicate that the solubility of TiO₂ in BaTiO₃ is <0.1 mol%.     

Subsolidus Equilibria in the TiO2-SnO2 System

The subsolidus miscibility gap for the TiO₂-SnO₂ system was redetermined. The critical temperature, 1430°C, is intermediate between that determined by Padurow, 1330°C, and that determined by Garcia and Speidel, 1475°C. Although the phase boundary is slightly asymmetric (the critical composition occurs at 47 mol% TiO₂), it fits the regular-solution model down to 1200°C. Calculations of the coherent spinodal using the regular-solution model indicated depression of the spinodal below T_c , by 105°, 310°, and 387° for composition fluctuations along the [001], <101>, and <100> directions, respectively. These depressions of the spinodal are much greater than those calculated by Stubican and Schultz; this discrepancy is believed to result from an error in the latter workers' calculations. During the present work, positive deviations from Vegard's law were found in this system. Both the magnitude and the sign of the deviation can be predicted using a theory based on nonlinear second-order elasticity.     

Helium Migration in TiO2-SiO2 Glasses

Helium permeability, diffusivity, and solubility were measured for a series of TiO₂-SiO₂ glasses containing up to 10.3 mol% TiO₂. The activation energies for helium permeation and diffusion decrease with increasing TiO₂ concentration. The enthalpy of solution is independent of composition, as are the infinite-temperature values for the permeability, diffusivity, and solubility. It is concluded that the observed changes in activation energies result from changes in the strain energy necessary to distort the R-O-R'bond. The average diffusional jump distance appears to be essentially independent of composition, as would be expected from the small changes observed in the molar volume as TiO₂ replaces SiO₂ in these glasses.     

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.     

Solution of MgO, CaO, and TiO2 in α-AI2O3

Atomistic simulation methods are used to predict the preferred solution mechanisms and their associated energies. Both full- and partial-charge models are discussed. It was found that defect clustering always results in a significant lowering of the solution energies but does not change the preferred solution reaction of any of the oxides. The large size of the Ca²⁺ ion results not only in a higher solution energy (lower solubility) for CaO compared to MgO but also to a different preferred compensation mechanism. The predicted energy for the cosolution of MgO and TiO₂ is dramatically smaller than for either oxide separately. Conversely, whereas solution of TiO₂ aids the solution of CaO, additions of CaO do not support TiO₂, Solution.     

A Study of the Phase Relations of ZrO2–TiO2 and ZrO2–TiO2–SiO2

The phase relations of the systems ZrO₂–TiO₂ and ZrO₂–TiO₂–SiO₂ were investigated. X-ray diffraction techniques served as the principal means of analysis. The binary system ZrO₂–TiO₂ was found to be one of partial solid solutions with no intermediate compounds. A eutectic point was found to exist at 50 to 55 weight % ZrO₂ and 1600°C. A preliminary investigation of the ternary system ZrO₂–TiO₂–SiO₂, although not extensive, resulted in a better understanding of this system, with a fairly accurate location of some of its boundary lines. A eutectic point was located at 2% ZrO₂, 10% TiO₂, and 88% SiO₂ at approximately 1500°C.     

Reactions in the System TiO2-P2O5

The system TiO₂-P₂O₅ was investigated in the compositional range TiO₂.P₂O₅ to 100% TiO₂. Two compounds exist, TiO₂.P₂O₅ and 5TiO₂.-2P₂O₅. TiO₂.P₂O₅ begins to lose P₂O₅ at 1400°C. and both fusion and vaporization proceed rapidly at 1500°C. 5TiO₂.2P₂O₆ melts congruently at 1260°± 3°C. to a glass which can be retained in substantial quantities at room temperature. Physical properties of certain compositions are described.     

Transformation Enthalpies of the TiO2 Polymorphs

The enthalpies of transformation of pure, well-characterized samples of brookite and anatase to rutile were determined by solution calorimetry in a 3Na₂O·4MoO₃ melt at 971 ±2 K. The experiments gave the following results: brookite→rutile, ΔH°₉₇₁= -0.17±0.09 kcal mol⁻¹; anatase → rutile, ΔH°₉₇₁= -0.78±0.20 kcal mol⁻¹.