Grain Boundary Mobility in Y2O3: Defect Mechanism and Dopant Effects

The effects of the dopants, Mg²⁺, Sr²⁺, Sc³⁺, Yb³⁺, Gd³⁺, La³⁺, Ti⁴⁺, Zr⁴⁺, Ce⁴⁺, and Nb⁵⁺, on the grain boundary mobility of dense Y₂O₃ have been investigated from 1500° to 1650°C. Parabolic grain growth has been observed in all cases over a grain size from 0.31 to 12.5 μm. Together with atmospheric effects, the results suggest that interstitial transport is the rate-limiting step for diffusive processes in Y₂O₃, which is also the case in CeO₂. The effect of solute drag cannot be ascertained but the anomalous effect of undersized dopants (Ti and Nb) on diffusion enhancement, previously reported in CeO₂, is again confirmed. Indications of very large binding energies between aliovalent dopants and oxygen defects are also observed. Overall, the most effective grain growth inhibitor is Zr⁴⁺, while the most potent grain growth promoter is Sr²⁺, both at 1.0% concentration.     

X-Ray Study of Phase Transitions in Ferroelectric PbNb2O6 and Related Materials

The phase transitions in PbNb₂O₆ and in compositions of the type Pb_1+x (B_xNb_1-x)O₆, where B = Ti⁴⁺, Zr⁴⁺, or Sn⁴⁺, have been investigated between 25° and 650°C. using X-ray and dilatometric techniques. The modified PbNb₂o₆ compositions possess orthorhombic PbNb₂O₆-type structure, with the additional Pb²⁺ ions occupying vacant lattice sites. The lattice parameters a and c expand and b contracts during heating until, at the ferroelectric Curie temperature, a and b suddenly coincide and c expands slightly. Besides this phase change at the Curie temperature, the nonstoichiometric compounds show an additional phase transition in the range 450° to 300°C. depending on composition. The intermediate phase of Pb_l+x(Ti₂Nb_1-z)₂O₆ appears to possess orthorhombic symmetry.     

Determination of the Cerium Oxidation State in Cerium Vanadate

Use of low-quality fuels in gas turbines can lead to vana-dium hot corrosion of stabilized-zirconia turbine blade coatings. The stabilizing oxide reacts with V₂O₅ in the melt, forming a vanadate, thus removing the stabilizer from the zirconia. To better understand the vanadation reaction of one such oxide, CeO₂, we have employed X-ray absorption spectroscopy to determine the oxidation state of the resulting vanadate, CeVO₄. A comparison of the cerium vanadate X-ray absorption spectra with Ce⁴⁺ and Ce³⁺ standards has established that the cerium valence in this compound is 3⁺. This result indicates that cerium is reduced during CeVO₄ formation and suggests that the vanadium reactant remains in the 5⁺ oxidation state.     

Synchrotron Radiation Ti-k XANES Study of TiO2─Y2O3-Stabilized Tetragonal Zirconia Polycrystals

Valence state and site symmetry of Ti ions in TiO₂–Y₂O₃–ZrO₂ powders with 2 mol% Y₂O₃ and 5, 10, 15, and 20 mol% TiO₂, respectively, are studied by X-ray absorption near-edge spectroscopy (XANES). Tetravalent Zr⁴⁺ ions are replaced predominantly by Ti⁴⁺ ions. Within the solubility region of Ti ions, a subsequent displacement of Ti ions from the center of symmetry is observed with increasing TiO₂ content in TiO₂–Y₂O₃-stabilized tetragonal ZrO₂ polycrystals (Ti-Y-TZP) under investigation. This behavior cannot be interpreted with a random substitution of Ti⁴⁺ ions on Zr⁴⁺ lattice sites. On the contrary, this correlation between the TiO₂ content in Ti-Y-TZP and the shift of Ti ions indicates an increasing interaction between the Ti ions with growing TiO₂ content, caused by a subsequent clustering of Ti ions.     

Sol–Gel Synthesis and Photocatalytic Activity of CeO2/TiO2 Nanocomposites

Uniform CeO₂ / TiO₂ composite nanoparticles with different Ce/Ti molar ratios have been successfully synthesized via the sol–gel method. The samples were characterized using differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The surface state analysis by means of X-ray photoelectron spectroscopy (XPS) shows that the Ti element mainly exists as a chemical state of Ti⁴⁺, while the Ce element exists as a mixture of Ce³⁺ and Ce⁴⁺ oxidation states. The photocatalytic degradation of methyl orange (MeO) in CeO₂ / TiO₂ suspension was investigated. The results indicate that the CeO₂/TiO₂ nanocomposites show higher photocatalytic activity than pure TiO₂. Photodegradation of MeO can be improved by increasing the Ce/Ti molar ratio in the initial 15 min.     

Transformation of Electron-Beam Physical Vapor-Deposited 8 wt% Yttria-Stabilized Zirconia Thermal Barrier Coatings

Yttria-stabilized (8.6 mol% YO_1.5) zirconia thermal barrier coatings evolve at high temperatures from the "non-transformable," metastable tetragonal-prime phase in their as-deposited condition to a mixture of the tetragonal and cubic phases. The kinetics of the transformation at 1200° and 1425°C are reported based on X-ray diffraction measurements. Complementary Raman spectroscopy measurements indicate a sharpening of the tetragonal bands at 263 and 465 cm⁻¹ that is attributed to a systematic decrease in disorder of the Y³⁺ and oxygen vacancies with annealing. No transformation to the monoclinic form of zirconia is observed immediately after high-temperature treatment. However, partial transformation to monoclinic occurs after a prolonged time (months) at room temperature in those samples treated at 1425°C, indicating the development of isothermal martensite.     

Enhanced Phase Stability and Photoluminescence of Eu3+ Modified t-ZrO2 Nanoparticles

Tetragonal ( t ) ZrO₂ nanoparticles have been obtained by a partial Eu³⁺→Zr⁴⁺ substitution, synthesized using a simple oxalate method at a moderate temperature of 650°C in air. The Eu³⁺ additive, 2 mol% used according to the optimal photoluminescence (PL), gives small crystallites of the sample. On raising the temperature further, the average crystallite size D grows slowly from 16 nm to a value as big as 49 nm at 1200°C. The Eu³⁺: t -ZrO₂ nanoparticles have a wide PL spectrum at room temperature in the visible to near-IR regions (550–730 nm) in the ⁵D₀→⁷F_J (Eu³⁺), J =1–4, electronic transitions. The intensity of the ⁵D₀→⁷F₄ group is as large as that of the characteristic ⁵D₀→⁷F₂ group of the spectrum in the forced electric-dipole allowed transitions. The enhanced t -ZrO₂ phase stability and wide PL can be attributed to the combined effects of an amorphous Eu³⁺-rich surface and part of the Eu³⁺ doping of ZrO₂ of small crystallites.     

Effect of a liquid Phase on Superplasticity of 2-moI%-Y203-StabiIlzed Tetragonal Zirconla Polycrystals

A small addition of CuO to 2-mol%-Y₂O₃-stabilized tetragonal zirconia polycrystals significantly enhances superplasticity by forming an amorhous grain-boundary phase containing primarily Cu⁺, Y³⁺, Zr⁴⁺, and O²⁻. This phase apparently melts at around 1130°C, but it already provides a fast diffusion path even below the melting temperature. There are abrupt changes in stress exponent, activation energy, and grain size exponent across the melting temperature. Superplasticity is diffusion-controlled below the melting temperature and is interfaced-controlled above that.     

Control of Grain-Boundary Pinning in Al2O3/ZrO2 Composites with Ce3+/Ce4+ Doping

The control of the microstructure of Ce-doped Al₂O₃/ZrO₂ componsites by the valence change of cerium ion has been demonstrated. Two distinctively different types of microstructure, large Al₂O₃ grains with intragranular ZrO₂ particles and small Al₂O₃ grains with intergranular ZrO₂ particles, can be obtained under identical presintering processing conditions. At doping levels greater than ∼ 3 mol% with respect to ZrO₂, Ce³⁺ raises the alumina grain-boundary to zirconia particle mobility ratio. This causes the breakaway of grain boundary from particles and the first type of microstructure. On the other hand, Ce⁴⁺ causes no breakaway and produces a normal intergranular ZrO₂ distribution. The dramatic effect of Ce³⁺ on the relative mobility ratio is found to be associated with fluxing of the glassy boundary phase and is likewise observed for other large trivalent cation dopants. The ZrO₂ second phase acts as a scavenger for these trivalent cations, provided their solubility limit in ZrO₂ is not exceeded.     

Synthesis of the Orthorhombic Phase of 2Y˙ZrO2

A mixture of tetragonal and monoclinic 2Y˙ZrO₂ (2 mol% Y₂O₃–ZrO₂) powder was treated from 400° to 800°C and from 4 to 7 GPa for 30 min. The products were identified by powder XRD, Raman spectroscopy, and TEM. Results indicated that an orthorhombic phase was synthesized at T=400° to 600°C and P>4 GPa. The lattice parameters were obtained as a=0.505, b=0.525, and c=0.509 nm; the density was 6.17 Mg/m³. The orthorhombic phase always coexisted with the tetragonal phase in the products. The amounts of the tetragonal phase before and after treatment remained largely unchanged, whereas the amount of new orthorhombic phase was nearly the same as the decreased amount of the monoclinic phase. It was assumed, therefore, that only the monoclinic phase transformed into the orthorhombic phase.     

EXAFS Study of Yttria-Stabilized Zirconia

The local structural environments of Y³⁺ and Zr⁴⁺ in 18 wt% Y₂O₃-stabilized zirconia were studied using extended X-ray absorption fine structure spectroscopy over the temperature range –120° to 770°C. The measured cation-oxygen distances reflect those of the parent oxides, with the mean Zr-O distance 0.017 nm shorter than the mean Y-O distance. The spread in the Zr–nearest-neighbor and Zr–next-nearest-neighbor distances is considerably larger than observed for Y³⁺. This result is attributed to the anion vacancies being preferentially sited adjacent to the smaller Zr⁴⁺ cation which, with ensuing relaxations, permits a closer contact between Zr⁴⁺ and its oxygen neighbors. Thus, the structural environment of these Zr⁴⁺ ions resembles that of the 7-coordinated Zr⁴⁺ in monoclinic zirconia. Increasing the temperature of the sample results in the local structural environments of the two cations becoming more alike, suggesting that increased anionic mobility leads to an increasingly random distribution of anion vacancies.     

Lattice Parameters, Ionic Conductivities, and Solubility Limits in Fluorite-Structure MO2 Oxide [M = Hf4+, Zr4+, Ce4+, Th4+, U4+] Solid Solutions

Changes in the lattice parameters of fluorite type MO₂ oxides (M = Hf⁴⁺, Zr⁴⁺, Ce⁴⁺, Th⁴⁺, U⁴⁺) due to the formation of solid solutions can be predicted by proposed empirical equations. The equations show the generalized relationship between dopant size and ionic conductivity in the binary systems of these oxides, illustrating that the smaller the difference between the dopant ionic radius and the critical dopant radius, the higher the conductivity. The solubility limit of the same periodic group elements in fluorite-structure MO₂ oxides decreaes linearly with the square of Vegard's slope for each solute as determined from the proposed equations.     

Exsolution of β-Ga2O3 Crystalline Solutions in the System MgAl2O3-Ga2O3

The subsolidus phase equilibrium diagram for the pseudobinary join MgAl₂O₄-Ga₂O₃ was determined. The shape of the exsolution boundary was obtained by heat-treating samples pre- equilibrated at 1600°C. Crystalline solubility of Ga₂O₃ in MgAl₂O₄ decreased from 73 mole % at 1600°C to 55 mole % at 1200°C. The crystalline solution was formed by the replacement of Mg²⁺ions by Ga³⁺ ions to produce a cation defect spinel. The phase precipitated was the mono-clinic δ-Ga₂O₃ (=δ-Al₂O₃ structure). Changes in the ratios of relative X-ray diffraction intensities indicated that the crystalline solutions also disorder with temperature.     

Core-Shell Structures in ZrO2-Modified BaTiO3 Ceramic

Pure BaTiO₃ exhibits a paraelectric-to-ferroelectric phase transition at 130°C. When stoichiometric BaTiO₃ is combined with 10 mol% ZrO₂, the relative permittivity (ε) changes to a broad, relatively insignificant temperature dependence, and the Curie point, T _c , is not sharply defined. However, the transition sharpens at T = 95°C when these samples are sintered for a longer period of 60 h. SEM, EDAX analysis coupled with TEM observation gives three types of core-shell structures of different microstructural characteristics which are related to the diffuse phase transition. Chemical inhomogeneity, due to Zr⁴⁺ distribution in the core-shell structure, is proposed to account for the diffuse phase transition behavior.     

Reaction Sequence and Microstructrual Development of CeO2-Doped Reaction-Bonded Mullite

A promising technique for the fabrication of mullite ceramics and mullite-matrix composites with low dimensional changes ("near-net-shape processing") is reaction bonding using Si metal and α-Al₂O₃ as starting materials, because sintering-induced shrinkage is compensated by Si-oxidation-induced volume expansion. A mullite reaction bonding (RBM) route which proceeds at much lower temperatures (lessthan equal to1350°C) than in conventional RBM systems (greaterthan equal to1500°C) is based on Ce doping which provides accelerated Si oxidation and mullite formation due to the formation of transient, low-viscosity Ce-Al-Si-O liquids. The present study shows that the required Ce-Al-Si-O liquids form in a reducing environment with Ce occurring as Ce³⁺. In an oxidizing environment, Ce is present as Ce⁴⁺, giving rise to precipitation of crystalline CeO₂. Ce³⁺ left and right arrow Ce⁴⁺ redox reactions in the temperature range under consideration appear to be controlled by the presence of nonoxidized Si in the samples. According to the present investigation the amount of CeO₂ added to the starting powders must be tailored carefully: Exaggerated CeO₂ content produces large amounts of low-viscosity Ce-Al-Si-O liquids which may have the disadvantage of excessive sealing of the open porosity. This slows the oxygen diffusion velocity into the specimen considerably, with the consequence that nonoxidized Si and a residual Ce-Al-Si-O glass coexist in the ceramics after processing. A solution to this problem is to simultaneously enhance mullite crystal growth through seeding which works against excessive liquid-phase-induced shrinkage of the samples. This in turn enables complete oxidation and recrystallization of all liquid phases.     

Raman Scattering Study of Cubic–Tetragonal Phase Transition in Zr1−xCexO2 Solid Solution

A structural phase transition between the cubic (space group, Fm 3 m) and tetragonal (space group, P 4₂ /nmc) phases in a zirconia–ceria solid solution (Zr_1−xCe_xO₂) has been observed by Raman spectroscopy. The cubic–tetragonal ( c–t" ) phase boundary in compositionally homogeneous samples exists at a composition X₀ (0.8 < X₀ < 0.9) at room temperature, where t " is defined as a tetragonal phase whose axial ratio c/a equals unity. The axial ratio c/a decreases with an increase of ceria concentration and becomes 1 at a composition X'₀ (0.65 < X'₀ < 0.7) at room temperature. The sample with a composition between X₀ and X'₀ is t " ZrO₂. By Raman scattering measurements at high temperatures, the tetragonal ( t" ) → cubic and cubic → tetragonal phase transitions occur above 400°C in Zr_0.2 Ce_0.8O₂ solid solution.     

Synthesis and Characterization of (Ce0.67Tb0.33)MnxMg1−xAl11O19 Phosphors Derived by Sol–Gel Processing

A (Ce_0.67Tb_0.33)Mn _x Mg_{1− x} Al₁₁O₁₉ phosphor powder was synthesized, using a simple sol–gel process, by mixing citric acid with CeO₂, Tb₄O₇, Al(NO₃)₃·9H₂O, Mg(OH)₂·4MgCO₃·6H₂O, and Mn(CH₃COO)₂. The phosphor crystallized completely at 1200°C, and the phosphor particle size was between 1 and 5 μm. The excitation spectrum was characteristic of Ce³⁺, while the emission spectrum was composed of lines from Tb³⁺ and Mn²⁺. The Mn²⁺ gave a green fluorescence band, and concentration quenching occurred when x > 0.10. The luminescent properties of the phosphor were explained by a configurational coordinate model.     

Raman Spectroscopic Study of Gallium-Doped Ba(Zn1/3Ta2/3)O3

Resonators of Ba(Zn_1/3Ta_2/3)O₃, sintered between 1450° and 1600°C, are characterized by Raman spectroscopy, X-ray diffraction, and scanning electron microscopy. The quality factors of the resonators are found to depend on sintering temperature, and at 1600°C there is evidence of Zn loss from the surface. The frequency of the A_1g Raman mode changes from 800.9 cm⁻¹ for a sample with Q = 80000 (2 GHz), to 794.5 cm⁻¹ when Q = 44000 (2 GHz). Changes in the position of this and other Raman modes are thought to be due to distortions of the oxygen octahedra, brought about by Zn loss. The presence of a BaTa₂O₆ phase at the surface is confirmed by XRD and SEM.     

In Situ Synthesis of Yttria-Stabilized Tetragonal Zirconia Polycrystal Powder Containing Dispersed Titanium Carbide by Selective Carbonization

Reaction thermodynamics was utilized to analyze the selective carbonization conditions of ZrO₂-TiO₂-Y₂O₃ ultrafine powder and to define the temperature range of the selective carbonization. The ZrO₂-TiO₂-Y₂O₃ powder was prepared by coprecipitation from a solution containing Zr⁴⁺, Ti⁴⁺, and Y³⁺. The powder was selectively carbonized at 1350°, 1450°, 1550°, and 1650°C, respectively, for 2 h under argon atmosphere with sucrose as the carbon source. The resulting product was analyzed by X-ray diffraction. The experimental results indicated that the ZrO₂-TiO₂-Y₂O₃ powder could be selectively carbonized in situ at 1450°C to form a carbonized powder which was composed of TiC and t -ZrO₂. It was also found that zirconium carbide could be formed at 1550°C, which is much lower than the carbonization temperature of ZrO₂ defined by thermodynamics.     

Ceria–Yttria-Stabilized Zirconia Composite Ceramic Systems for Applications as Low-Temperature Electrolytes

Ceramic samples of Ce_{1− x} Gd _x O_{2− y} and yttria-stabilized zirconia (YSZ) were prepared using solid-state methods. Polished faces of disks of these materials were held in intimate contact in a reaction cell at temperatures ranging from 1000° to 1300°C for durations up to 72 h. XRD, SEM, and microprobe Raman techniques were used to analyze the resulting reactions and ion diffusion. No reaction was observed at 1000°C after 72 h between the 10-mol%- and 20-mol%-Gd-doped CeO₂ and the YSZ. However, at 1300°C, a mixing region 25 μ m wide occurred, resulting in a cubic phase, where Zr⁴⁺ ions diffused into the CeO₂.