Synthesis of ZrO2 and Y2O3-Doped ZrO2 Thin Films Using Self-Assembled Monolayers

Undoped or Y₂O₃-doped ZrO₂ thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO₄)·4H₄O) solutions in the presence of HCl at 70°C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- ( t -) ZrO₂ and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500°C led to complete crystallization to t -ZrO₂. Amorphous Y₂O₃-containing ZrO₂ films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y₂(SO₄)₃8·H₂O), and urea (NH₂CONH₂) at pH 2.2–3.0 at 80°C. These films also were fully crystalline after annealing at 500°C.     

Sintering, Microstructure, Hardness, and Fracture Toughness Behavior of Y2O3-CeO2-ZrO2

A wet-chemical approach is applied to derive fine powders with compositions 11 mol% CeO₂-ZrO₂, 1 mol% YO_1.5-10 mol% CeO₂-ZrO₂, 12 mol% CeO₂-ZrO₂, and 2 mol% YO_1.5-10 mol% CeO₂-ZrO₂ by the coprecipitation method. The characteristics of the as-derived powders are evaluated through thermal analysis and electron microscopy. The sintering behavior of the calcined powders is carried out at 1400° and 1500°C for 1 to 10 h. Sintered density higher than 98% of theoretical is achieved for sintering at 1400°C for several hours. The as-sintered density dependence on the sintering condition is related to the extent of tetragonal-to-monoclinic phase transformation as well as the associated microcracks. Partial substitution by Y₂O₃ in CeO₂-ZrO₂ results in reduced grain size and tends to stabilize the tetragonal structure. Y₂O₃ is more effective than CeO₂ with respect to the grain size refinement and tetragonal stability. In addition, Y₂O₃ substitution in CeO₂-ZrO₂ increases the hardness, while it decreases the fracture toughness.     

Ionic Conductivity of Cubic Solid Solutions in the System CaO—Y2O3—ZrO2

The ionic conductivity of cubic solid solutions in the system CaO -Y₂O₃-ZrO₂ was examined. Particular Y₂O₃-ZrO₂ binary compositions were more conductive at elevated temperatures (>600°C) than either CaO-ZrO₂ binary or CaO-Y₂O₃-ZrO₂ ternary compositions. The higher ionic conductivity appears to be related to a lower activation energy rather than to the number of oxygen vacancies dictated by composition. Those compositions of highest conductivity lie close to the cubic-monoclinic solid-solution phase boundary. Conductivity-temperature data are presented that indicate a reversible order-disorder transition for Y₂O₃-ZrO₂ cubic solid solutions containing 20 and 25 mole % Y₂O₃. The transference number for the oxygen ion at 1000°C for Y₂O₂-ZrO₂ cubic solid solutions is greater than 0.99.     

Phase Transformation in Y2O3-Partially-Stabilized ZrO2 Polycrystals of Various Grain Sizes during Low-Temperature Aging in Water

ZrO₂-2 mol% Y₂O₃ crystals with average grain sizes from 0.51 to 0.96 µm were prepared by sintering in air at 1400°C for 2 to 100 h. The tetragonal-to-monoclinic phase transformation associated with the low-temperature degradation was investigated to clarify how the presence of water directly affects the influence of grain size on transformation. The specimens were exposed to water at 80–120°C, a temperature range in which transformation by thermal activation is difficult in the absence of water. Contrary to expectations, this type of low-temperature transformation did not accelerate monotonously with increasing grain size. Instead, the amount of phase transformation first decreased, reaching a constant value, and then increased with increasing grain size. Such interesting results can be explained satisfactorily by the combined influences of grain size on the nucleation process, because of preferential dissolution of yttrium at the grain boundaries, and the intrinsic transformability of Y₂O₃-doped tetragonal ZrO₂ grains.     

Fracture Toughness of Al2O3-Particle-Dispersed Y2O3-Partially Stabilized Zirconia

The fracture toughness of 3 mol% Y₂O₃-ZrO₂ (3Y-PSZ) composites containing 10–30 vol% Al₂O₃ with different particle sizes was investigated. It was found that Al₂O₃ dispersion of up to 30 vol% increased the fracture toughness by 17% to 30%, and the toughness increase was more remarkable in the composite dispersed with Al₂O₃ particles of larger sizes. By combining the effects of the dispersion toughening and phase transformation toughening, the toughness change in the present materials was theoretically predicted, which was in good agreement with the experimental data.     

Influence of the Y2O3 Content and Temperature on the Mechanical Properties of Melt-Grown Al2O3–ZrO2 Eutectics

The effect of Y₂O₃ content on the flexure strength of melt-grown Al₂O₃–ZrO₂ eutectics was studied in a temperature range of 25°–1427°C. The processing conditions were carefully controlled to obtain a constant microstructure independent of Y₂O₃ content. The rod microstructure was made up of alternating bands of fine and coarse dispersions of irregular ZrO₂ platelets oriented along the growth axis and embedded in the continuous Al₂O₃ matrix. The highest flexure strength at ambient temperature was found in the material with 3 mol% Y₂O₃ in relation to ZrO₂(Y₂O₃). Higher Y₂O₃ content did not substantially modify the mechanical response; however, materials with 0.5 mol% presented a significant degradation in the flexure strength because of the presence of large defects. They were nucleated at the Al₂O₃–ZrO₂ interface during the martensitic transformation of ZrO₂ on cooling and propagated into the Al₂O₃ matrix driven by the tensile residual stresses generated by the transformation. The material with 3 mol% Y₂O₃ retained 80% of the flexure strength at 1427°C, whereas the mechanical properties of the eutectic with 0.5 mol% Y₂O₃ dropped rapidly with temperature as a result of extensive microcracking.     

Growth of α-AI2O3 Platelets in the HF-γy-AI2O3 System

In the presence of a fluorine mineralizer, highly aggregated, <5 μm α-Al₂O₃ platelet particles form by vapor transport during the thermal transformation of γ-alumina. Platelet aggregation was determined to occur by platelet inter-growth and by edge nucleation on primary α-Al₂0₃ platelets. The addition of 10¹⁰α-alumina seed particles/cm³γ–Al₂O₃ resulted in the development of discrete particles during the initial stage of transformation. Impingement of the growing platelets during the latter stage of transformation, however, resulted in intergrowth, a process which was not changed by seeding. Particle size distribution broadening was observed to increase with increasing HF and H₂O concentrations because vapor reactant supersaturation increases the degree of edge nucleation. When initially low HF and H₂O concentrations were used in seeded systems, however, essentially aggregate-free α-Al₂O₃ platelets of 10–15 μm were obtained.     

Studies on 4CaOAl2.O3.13H2O and the Related Natural Mineral Hydrocalumite

Single-crystal X-ray and electron-diffraction studies show the existence in one polymorph of 4CaO.Al₂O₃. 13H₂O of a hexagonal structural element with α= 5.74 a.u., c = 7.92 a. u. and atomic contents Ca₂(OH)₇- 3H₂O. These structural elements are stacked in a complex way and there are probably two or more poly-types as in SiC or ZnS. Hydrocalumite is closely related to 4CaO.A1₂O₃.13H₂O, from which it is derived by substitution of CO₃^2-for 20H^-+ 3H₂O once in every eight structural elements; similar substitutions explain the existence of compounds of the types 3CaO Al₂O₃.Ca Y ₂- xH₂O and 3CaO Al₂O₃ Ca Y xH₂O. On dehydration, 4CaO.Al₂O₃.13H₂O first loses molecular water and undergoes stacking changes and shrinkage along c. At 150° to 250°C., Ca(OH)₂ and 4CaO.3Al₂O₃.3H₂O are formed and, by 1000°C., CaO and 12CaO.7Al₂O₈. The dehydration of hydrocalumite follows a similar course, but no 4CaO.3Al₂O₃.3H₂O is formed.     

Physical Properties and Structure of rf-Sputtered Amorphous Films in the System Al2O3–Y2O3

Amorphous films in the system Al₂O₃–Y₂O₃ were prepared by the rf sputtering method in the range of 0–76 mol% Y₂O₃, and their density, refractive index, and elastic constants were measured. All of the physical properties of the amorphous Al₂O₃–Y₂O₃ films had a similar compositional dependence; that is, they increased continuously, but not linearly with increasing Y₂O₃ content. To confirm the coordination states of aluminum and yttrium ions in the amorphous Al₂O₃–Y₂O₃ films, the Al K α X-ray emission spectra and the X-ray absorption near edge structures (XANES) were measured. The average coordination number of aluminum ions in the amorphous films containing up to about 40 mol% Y₂O₃ content was 5, that is a mixture of 4-fold- and 6-fold-coordinated states. In the region of more than about 50 mol% Y₂O₃, the fraction of the 6-fold-coordinated aluminum ions increased with increasing Y₂O₃ content, while the results led to the conclusion that the coordination number of yttrium ions was always 6, regardless of composition. These results indicate that, in amorphous films in the system Al₂O₃–Y₂O₃, the change of the coordination state of aluminum ions has an important effect on physical properties.     

Hydration of 3CaO·Al2O3 and 3CaO·Al2O3+] Gypsum With and Without CaCl2

Paste samples of tricalcium aluminate alone, with CaCl₂, with gypsum, and with gypsum and CaCl₂ were hydrated for up to 6 months and the hydration products characterized by SEM, XRD, and DTA. Tricalcium aluminate hydrated initially to a hexagonal hydroaluminate phase which then changed to the cubic form; the transformation rate depended on the size and shape of the sample and on temperature. The addition of CaCl₂ to tricalcium aluminate resulted in the formation of 3CaO · Al₂O₃· CaCl₂·10H₂O and 4CaO · Al₂O₃· 13H₂O, or a solid solution of the two. The chloride retarded the formation of the cubic phase 3CaO · Al₂O₃· 6H₂O; the addition of gypsum resulted in the formation of monosulfoaluminate with a minor amount of ettringite. When chloride was added to tricalcium aluminate and gypsum, more ettringite was formed, although 3CaO · Al₂O₃· CaSO₄· 12H₂O and 3CaO · Al₂O₃· CaCl₂· 10H₂O were the main hydration products.     

Influence of Citric Acid on Reactions in the System 3CaO·Al2O3-CaSO4·2H2O-CaO-H2O

The influence of citric acid on paste hydration of 3CaO· Al₂O₃ in the presence of CaSO₄·2H₂O and Ca(OH)₂ was studied using X-ray diffraction, scanning electron microscopy, and conduction calorimetry. The time at which the citric acid is added (either prior to or with the mixing water) determines how it affects the reactivity of the aluminate. Immediately after the paste is gaged citric acid promotes a more rapid reaction, but later reactions are retarded. Hexagonal calcium aluminate hydrates, ettringite, and monosulfate were all detected as early hydration products. The influence of citric acid on the hydration of 3CaO·Al₂O₃ slabs immersed in saturated CaSO₄·2H₂O solutions was also studied and a reaction scheme proposed.     

Interfaces in Oriented Al2O3-ZrO2 (Y2O3) Eutectics

Oriented samples of Al₂O₃-ZrO₂ (Y₂O₃) eutectics consisting of an alumina matrix with zirconia dispersoids were grown by directional solidification. Preferred growth directions and epitaxial relations were determined from X-ray and electron diffraction analyses. Imaging of interfaces was performed by high-resolution transmission electron microscopy on oriented platelets. Semicoherent interfaces were observed with faceting along crystallographic planes of both phases.     

Formation of Sm2+ lons in Sol-Gel-Derived Glasses of the System Na2 O-Al2O3-SiO2

Samarium ions (Sm²⁺) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na₂O-Al₂O₃SiO₂ synthesized by the hydrolysis of Si(OC₂H₅)₄, Al(OC₄H₉)₃, CH₃ COONa, and SmCl₃·6H₂O were heated in air at 500°C, then reacted with H₂ gas to form Sm²⁺ ions. Whereas Al³⁺ ions effectively dispersed the Sm³⁺ ions in the glass structure, Na⁺ ions were not effective. The Al₂O₃-SiO₂ glasses proved appropriate for reacting the Sm³⁺ ions with H₂ gas and exhibited the intense photoluminescence of Sm²⁺ ions. The reaction of Sm³⁺ ions with H₂ in the Al₂O₂-SiO₂ glasses was determined by first-order kinetics, and the activation energy equaled 95 kJ/mol. At 800°C, the maximum photoluminescence of the Sm²⁺ ions was achieved within 20 min.     

Phase Stability, Phase Transformation Kinetics, and Conductivity of Y2O3—Bi2O3 Solid Electrolytes Containing Aliovalent Dopants

Single-phase, cubic solid solutions of baseline composition 25% Y₂O₃—75% Bi₂O₃ with and without aliovalent dopants were fabricated by pressureless sintering of powder compacts. CaO, SrO, ZrO₂, or ThO₂ was added as an aliovalent dopant. Sintered samples were annealed between 600° and 650°C for up to 4000 h. Samples doped with ZrO₂ or ThO₂ remained cubic, depending upon the dopant concentration, even after long-term annealing. By contrast, undoped, CaO-doped, and SrO-doped samples transformed to the low-temperature, rhombohedral phase within ∼ 200 h. Conductivity measurements showed no degradation of conductivity in samples that did not undergo the transformation. In samples that underwent the transformation, a substantial decrease in conductivity occurred. The enhanced stability of the ZrO₂- and ThO₂-doped samples is rationalized on the basis of suppressed interdiffusion on the cation sublattice.     

The Structure of Some B2O3-H2O Glasses

Boron oxide glasses with compositions corresponding to B₂O₃, B₂O₃.0.42H₂O, B₂O₃.0.50H₂O, and B₂O₃.0.63H₂) have been prepared and their structures have been studied. Diffractometric X-ray scattering measurements have been made, and from these, radial distribution functions have been computed. Comparison of the radial distribution functions indicates that the fundamental triangular coordination characteristic of vitreous B₂O₃ is maintained in the water-containing glasses. Consideration of the results of complementary infrared and nuclear magnetic resonance studies along with preliminary results of physical property measurements indicates that the glasses of high water content are heterogeneous. It is probable that disordered regions of high hydrogen bond density, approaching HBO₂ in composition, are embedded in a matrix approximating vitreous B₂O₃.     

Er-Doped Y2O3 Nanoparticles: A Comparison of Different Synthesis Methods

Nanoparticles of erbium-doped yttria (Er:Y₂O₃) are important precursors to transparent ceramics for high-power solid-state lasers systems. As structure influences properties and, subsequently, performance the purpose of this work is to compare the morphological and chemical nature of the nanoparticles synthesized using two common methods: solution precipitation and combustion synthesis. A thorough characterization of as-prepared and calcined powders was performed using Fourier transform infrared spectroscopy, X-ray diffraction, conventional and high-resolution transmission electron microscopy, and Brunauer–Emmet–Teller methods. Solution precipitation was found to lead to two different precursor compositions (yttrium carbonate or yttrium hydroxide) depending on the precipitating reagent whereas combustion synthesis yielded only phase-pure, cubic Er:Y₂O₃. The hydroxide precipitation and combustion synthesis methods exhibited agglomerated particles with low surface area after calcining the precursors at 900°C. The addition of a small amount of ammonium sulfate during combustion synthesis was found to reduce the level of agglomeration, resultant particle size, and degree of crystallinity of the calcined Er:Y₂O₃ nanoparticles. The amount of carbon dioxide (CO₂) and water (H₂O) on the surface of the Er:Y₂O₃ powders is dependent on the powder surface area, however, increasing levels of gas absorption on the particle surfaces do not have a detrimental effect on the sinterability. The sintered density increases with increasing surface area and decreasing agglomeration.     

The System CaO-Al2O3-H2O

Phase equilibria have been determined in the system CaO-Al₂O₃-H₂O in the temperature range 100° to 1000°C. under water pressures of up to 3000 atmospheres. Only three hydrated phases are formed stably in the system: Ca(OH)₂, 3CaO·Al₂O₃·6H₂O, and 4CaO·3Al₂O₃-3H₂O. Pressure-temperature curves delineating the equilibrium decomposition of each of these phases have been determined, and some ther-mochemical data have been deduced therefrom. It has been established that both the compounds CaO·Al₂O₃ and 3CaO·Al₂O₃ have a minimum temperature of stability which is above 1000°C. The relevance of the new data to some aspects of cement chemistry is discussed.     

Strength of Hot Isostatically Pressed Si3N4 After Heat Treatment in Ar-O2 and H2-H2O

The effects of heat treatment in Ar-O₂ and H₂-H₂O atmospheres on the flexural strength of hot isostatically pressed Si₃N₄ were investigated. Increases in room-temperature strength, to values significantly above that of the aspolished material, were observed when the Si₃N₄ was exposed at 1400°C to (1) H₂ with water vapor pressure ( P _H2O) greater than 1 × 10⁻⁴ MPa or (2) Ar with oxygen partial pressure ( P _O2) of between 7 × 10⁻⁶ and 1.5 × 10⁻⁵ MPa. However, the strength of the material was degraded when the P _H2O in H₂ was lower than 1 × 10⁻⁴ MPa, and essentially unaffected when the P _O2 in Ar was higher than 1.5 × 10⁻⁵ MPa. We suggest that the observed strength increases are the result of strength-limiting surface flaws being healed by a Y₂Si₂O₇ layer formed during exposure.     

High-Temperature Environmental Stability of the Compounds in the Al2O3–Y2O3 System

Heat treatments in several environments were performed on a series of compounds in the Al₂O₃ and Y₂O₃ system: Al₂O₃Y₃Al₅O₁₂ eutectic, Y₃Al₅O₁₂, YAlO₃, Y₄Al₂O₉, and Y₂O₃. The yttrium aluminates were found to be stable at high temperatures under vacuum and in air. However, when they were heat-treated under vacuum in proximity to SiC, degradation was observed. This was found to be primarily a result of carbothermal reduction. In a similarly reducing environment without Si, the yttrium aluminates, and Al₂O₃ and Y₂O₃, all exhibited degradation by carbothermal reduction. Based upon the experimental results, a degradation mechanism for yttrium aluminates was proposed.     

Stable and Metastable Equilibria in the Systems Y2O2-Al2O3, and Gd2O3-Fe2O3

The phase equilibrium relations in the systems Y₂O₃-Al₂O₃ and Gd₂O₃-Fe₂O₃ were examined. Each system has two stable binary compounds. A 3:s molar ratio garnet-type compound exists in both systems. The 1:1 distorted perovskite structure is stable in the system Gd₂O₃-Fe₂O₃ but only metastable in the system Y₂O₃-AI₂O₃. This interesting example of metastable formation and persistence of a compound with ions of high Z/r values explains the discrepancies in the literature on the structure of the composition YA1O₃. A new 2:1 molar ratio cubic phase has been found in the system Y₂O₃-A1₂O₃. Since silicon can be completely substituted for aluminum in this compound, the aluminum ions are presumably in fourfold coordination.