Prediction of Rare-Earth A2Hf2O7 Pyrochlore Phases

Within the series of A₂O₃-HfO₂ phase diagrams (A ranges in cationic radius from Lu³⁺ to La³⁺), only those from Gd₂Hf₂O₇ to La₂Hf₂O₇ are known to exhibit a pyrochlore phase field. For A cations smaller than Gd³⁺, only a disordered fluorite phase field exists. Disorder energies for the entire series of pyrochlore oxides have been determined via atomistic simulation. These energies can be correlated to the order-disorder temperatures from the phase diagrams. Consequently, we predict the existence of hitherto unobserved pyrochlores: Dy₂Hf₂O₇, Ho₂Hf₂O₇, and Er₂Hf₂O₇.     

Standard Enthalpy of Formation of Lanthanum Zirconate

The enthalpy of formation of lanthanum zirconate, La₂Zr₂O₇, which is shown to have a distorted pyrochlore structure, was determined. High-temperature solution calorimetry in molten lead borate was used to determine the heat of formation from the constituent oxides as −135.8 ± 6.4 kJ/mol at 974 K. Using additional data on the enthalpies of formation of the oxides and heat contents, this value was converted to a standard enthalpy of formation from the elements: Δ_fH°_298.15=−4130.4 ± 6.8 kJ/mol.     

Study of Nonstoichiometry of 〈U1–zGdzO2±x〉

The extensive nonstoichiometry in the 〈U_{1– z} Gd _z O_{2± x} 〉 † phase was investigated experimentally and the data are represented by a chemical thermodynamic method. The experimental ranges of temperature, oxygen potential, and z were 1273 to 1773 K, 0 to −600 kJ/mol, and 0.1 to 0.8, respectively. For hypostoichiometry, ideal-solution thermodynamics for the equilibrium 3Gd_4/3O₂+ 4UO₂+ (O₂) = 6U_2/3Gd_2/3O_8/3 were used to represent the experimental data, while for hyperstoichiometry a nonideal solution was used for the equilibrium 4UO₂+ (O₂) = 2U₂O₅. The wide ranges in x and z led to an improvement of the previous analysis of literature data and led to partial molal Gibbs free energy values that are useful for any thermodynamic calculation involving the phase.     

Phase Relations In The Pseudo-Ternary System La2O3–SrO–Fe2O3

The phase relations in the pseudo-ternary system La₂O₃–SrO–Fe₂O₃ have been investigated in air. Isothermal sections at 1100° and 1300°C are presented based on X-ray diffraction and thermal analysis of annealed samples. Extended solid solubility was observed for the compounds Sr _{n +1− v} La _v Fe _n O_{3 n +1−δ} ( n =1, 2, 3, and ∞) and Sr_{1− x} La _x Fe₁₂O₁₉, while only limited solubility of La in Sr_{4− z} La _z Fe₆O_13±δ was observed. At high Fe₂O₃ content, a liquid with low La₂O₃ content was stable at 1300°C.     

High-Temperature Creep Behavior of Mixed Conducting La0.5Sr0.5Fe1−xCoxO3-δ (0.5≤x≤1) Materials

Steady-state compressive creep rate of La_0.5Sr_0.5Fe_0.5Co_0.5O_3−δ (LSFC) and La_0.5Sr_0.5CoO_3−δ (LSC) is reported in the temperature region 900°–1050°C and stress range 5–28 MPa. The stress exponents for the two materials were 1.71±0.18 and 1.24±0.15, respectively. The activation energy for creep was considerably higher for LSC (619±56 kJ/mol) than for LSFC (392±28 kJ/mol). The grain size exponent for LSC was 1.28±0.14. Considerably higher creep rates were observed for both materials in N₂ compared with air. Relaxation by creep of chemical-induced stresses in oxygen-permeable membranes is addressed, especially at low partial pressure of oxygen.     

Phase Equilibrium and Martensitic Transformation in Lanthana-Doped Zirconia

The system ZrO₂-La₂O₃ has been studied in the 0 to 15 mol% La₂O₃ range using X-ray diffraction and thermal analysis. Two kinds of diagrams were elaborated: First is a phase equilibrium diagram where the eutectoid decomposition of ZrO_{2, ss} (T) → ZrO_{2, ss} (M) + Py _ss occurs at 1100°C and 0.75 mol% La₂O₃ (Py is the pyrochlore compound Zr₂La₂O₇). The maximum solubility of La₂O₃ in ZrO_{2, ss} (M) is 0.5 mol% at room temperature. Second, a nonequilibrium diagram is determined showing the correlations between grain size, La₂O₃ content, and the martensitic transformation temperature start ( Ms ).     

X-ray Diffraction and 151Eu Mössbauer Spectroscopic Study of the Hf1−xEuxO2−x/2(0 ≤x≤ 1.0) System

Powder X-ray diffractometry (XRD) and ¹⁵¹Eu Mössbauer spectroscopy were performed for samples prepared in the temperature range 1500–1500°C for the hafnia–europia (HfO₂–Eu₂O₃) system Eu _x Hf_{1− x} O_{2− x /2}(0 ≤ x ≤ 1.0). The XRD results showed that two types of solid solution phases formed in the composition range 0.25 ≤ x ≤ 0.725: an ordered pyrochlore-type phase in the middle-composition range (0.45 < x < 0.575) and a disordered fluorite-type phase, enveloping the pyrochlore-type phase on both sides, in the composition ranges 0.25 ≤ x ≤ 0.40 and 0.60 ≤ x ≤ 0.725. ¹⁵¹Eu Mössbauer spectroscopy sensitively probes local environmental changes around trivalent europium (Eu³⁺) caused by the formation of these solid solution phases. In addition to the broad, single Mössbauer spectra observed in this study for the Eu³⁺, the values of isomer shift (IS) exhibited a pronounced minimum in the neighborhood of the stoichiometric pyrochlore phase ( x ≈ 0.5). Such IS behavior of Eu³⁺ was interpreted based on the XRD crystallographic information that the ordered pyrochlore phase has a longer (in fact, the longest) average Eu–O bond length than those of the disordered fluorite phases on both sides or the monoclinic (and C-type) Eu₂O₃at x = 1.0.     

Low-Thermal-Conductivity Rare-Earth Zirconates for Potential Thermal-Barrier-Coating Applications

Rare-earth zirconates have been identified as a class of low-thermal-conductivity ceramics for possible use in thermal barrier coatings (TBCs) for gas-turbine engine applications. To document and compare the thermal conductivities of important rare-earth zirconates, we have measured the thermal conductivities of the following hot-pressed ceramics: (i) Gd₂Zr₂O₇ (pyrochlore phase), (ii) Gd₂Zr₂O₇ (fluorite phase), (iii) Gd_2.58Zr_1.57O₇ (fluorite phase), (iv) Nd₂Zr₂O₇ (pyrochlore phase), and (v) Sm₂Zr₂O₇ (pyrochlore phase). We have also measured the thermal conductivity of pressureless-sintered 7 wt% yttria-stabilized zirconia (7YSZ)—the commonly used composition in current TBCs. All rare-earth zirconates investigated here showed nearly identical thermal conductivities, all of which were ∼30% lower than the thermal conductivity of 7YSZ in the temperature range 25°–700°C. This finding is discussed qualitatively with reference to thermal-conductivity theory.     

Direct Calorimetric Measurement of Enthalpies of Phase Transitions at 2000°–2400°C in Yttria and Zirconia

High-temperature differential thermal analysis provided data on phase transitions in zirconia and yttria. The tetragonal form of ZrO₂ transforms to the cubic fluorite structure at 2311°±15°C with an enthalpy of 3.4±3.1 kJ/mol. Cubic C-type Y₂O₃ transforms, probably to the fluorite structure, at 2308°±15°C with Δ H =47.7±3.0 kJ/mol. This high-temperature polymorph melts at 2382°±15°C with an enthalpy of fusion of 35.6±3.0 kJ/mol.     

Immiscibility and the System Lanthanum Oxide–Boric Oxide

The phase equilibrium diagram for the system La₂O₃-B₂O₃ has been determined experimentally. The compounds La₂O₃-3B₂O₃and La₂O₃-B₂O₃ melt congruently at 1141°± 5°C. and 1660°± 15°C, respectively. At 1488°± 5°C, La₂O₃-B₂O₃ inverts from the aragonite-type structure to a high-temperature form. Trilanthanum borate, 3La₂O₃ B₂O₃, melts incongruently at 1386°± 5°C. to give liquid and La₂O₃. No solid solutions exist in the system. A region of liquid immiscibility exists in the system and extends at 1136°± 5°C. from almost pure B₂O₃ to 21.5 mole % La₂O₃. The experimental value for the extent of immiscibility agrees with that calculated from theoretical considerations. A second method for estimating immiscibility in the system is demonstrated, which requires experimentally only the determination of the index of refraction of the modifier-rich liquid. Principles governing immiscibility are discussed.     

Energetics of La2O3–HfO2–SiO2 Glasses

A series of La₂O₃–HfO₂–SiO₂ glasses, approximately along the join 0.73SiO₂–0.27( x HfO₂–(1− x )La₂O₃), 0< x <0.3), was prepared using containerless processing techniques (aerodynamic levitation combined with laser heating in oxygen). The enthalpy of formation and enthalpy of vitrification at 25°C were obtained from drop solution calorimetry of these glasses and appropriate crystalline compounds in a molten lead borate (2PbO–B₂O₃) solvent at 702°C. The enthalpy of formation from crystalline oxides was exothermic and became less exothermic with increasing HfO₂ content. Heat contents were measured by transposed temperature drop calorimetry and depended linearly on the HfO₂ content. Differential scanning calorimetry showed that both the onset glass transition and the onset crystallization temperature of these glasses increased with increasing HfO₂ content. Upon slow cooling in air, the glasses crystallized to a mixture of baddeleyite, cristobalite, lanthanum disilicate, and hafnon.     

Preparation and Electrical Properties of New Oxide Ion Conductors Ce6−xGdxMoO15−δ (0.0≤x≤1.8)

A series of oxide ion conductors Ce_{6− x} Gd _x MoO_15−δ (0.0≤ x ≤1.8) have been prepared by the sol–gel method. Their properties were characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Raman, IR, X-ray photoelectron spectroscopy (XPS), and AC impedance spectroscopy. The XRD patterns showed that the materials were single phase with a cubic fluorite structure. The conductivity of Ce_{6− x} Gd _x MoO_15−δ increases as x increases and reaches the maximum at x =0.15. The conductivity of Ce_4.5Gd_1.5MoO_15−δ is σ_t=3.6 × 10⁻³ S/cm at 700°C, which is higher than that of Ce_4.5/6Gd_1.5/6O_2−δ (σ_t=2.6 × 10⁻³ S/cm), and the corresponding activation energy of Ce_4.5Gd_1.5MoO_15−δ (0.92 eV) is lower than that of Ce_4.5/6Gd_1.5/6O_2−δ (1.18 eV).     

The System Hafnia-Samaria

The phase relations in the system HfO₂-Sm₂O₃ were studied by high-temperature and room-temperature X-ray diffraction. The areas of existence of the solid solutions based on HfO₂, Sm₂Hf₂O₇, and Sm₂O₃ were determined using the lattice parameter method. Also, the influence of small additions of Sm₂O₃ on the monoclinic-tetragonal transformation temperature of hafnia was studied. A tentative phase diagram is proposed.     

Vaporization Studies of the La2O3–Ga2O3 System

The vaporization of the samples of the compositions Ga₂O₃+ LaGaO₃, LaGaO₃+ La₄Ga₂O₉, and La₄Ga₂O₉+ La₂O₃ was investigated using Knudsen effusion mass spectrometry in the temperature range 1494–1937 K. The partial pressures of the gaseous species O₂, Ga, GaO, Ga₂O, and LaO were determined over the samples investigated. The equilibrium partial pressures were used for the calculation of the thermodynamic activities of the components at 1700 K. Gibbs energies of formation of LaGaO₃( s ) and La₄Ga₂O₉( s ) at 1700 K from the component oxides were derived from the thermodynamic activities as −46.4 ± 4.7 and −99.2 ± 7.9 kJ·mol⁻¹, respectively. The results were compared with the literature data obtained using other methods.     

Densification, Structure, and Thermophysical Properties of Ytterbium–Gadolinium Zirconate Ceramics

(Yb _x Gd_{1− x} )₂Zr₂O₇ (0≤ x ≤1.0) ceramic powders synthesized with the chemical-coprecipitation and calcination method were pressureless-sintered at 1550–1700°C to develop new thermal barrier oxides with a lower thermal conductivity than yttria-stabilized zirconia ceramics. (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics exhibit a defective fluorite-type structure. The linear thermal expansion coefficients of (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics increase with increasing temperature from room temperature to 1400°C. The measured thermal conductivity of (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics first gradually decrease with increasing temperature and then slightly increase above 800°C because of the increased radiation contribution. YbGdZr₂O₇ ceramics have the lowest thermal conductivity among all the composition combinations studied.     

Effect of La Doping on the Phase Conversion, Microstructure Change, and Electrical Properties of Bi2Fe4O9 Ceramics

Undoped and La-doped Bi₂Fe₄O₉ ceramics were synthesized using a soft chemical method. It is observed that in calcining La-doped Bi₂Fe₄O₉, Bi(La)FeO₃ phase rather than Bi_{2− x} La _x Fe₄O₉ gradually increases with increasing La doping content. The phase conversion from mullite-type structure of Bi₂Fe₄O₉ to rhombohedrally distorted perovskite one of Bi(La)FeO₃ with increasing La doping content indicates that La doping can stabilize the structure of BiFeO₃. This is further evidenced that Bi₂Fe₄O₉ can be directly converted to Bi(La)FeO₃ by heating the mixtures of nominal composition of Bi₂Fe₄O₉/ x La₂O₃. Furthermore, the microstructure changes and the room temperature hysteresis loops and leakage current for Bi_{2− x} La _x Fe₄O₉ with x =0 and 0.02 were characterized.     

Phase Relations and Ordering in the System Erbia-Hafnia

The system erbia-hafnia was investigated using thermal expansion measurements and room-temperature X-ray diffraction of quenched and annealed samples. The range of existence of the solid solutions based on HfO₂ and Er₂O₃ was determined by the precision lattice parameter method. Three compounds with hexagonal structure are reported: the first is an ordered fluorite-related phase with the ideal formula Er₄Hf₃O₁₂ and decomposes with increasing temperature at ∼1500°C into a solid solution of the fluorite type; the second is formed at ∼55 mol% Er₂O₃, corresponding closely to the formula Er₅Hf₂O_11.5, and undergoes a transformation at ∼1650°C into cubic solid solutions to fluorite and C type. The third compound is formed within the concentration range between 60 and 90 mol% Er₂O₃. This compound, Er₆HfO₁₁, decomposes at ∼1700°C into a cubic solid solution of the C type. A proposed phase diagram for the system erbia-hafnia is presented.     

Vaporization of LaCrO3: Partial and Integral Thermodynamic Properties

The vaporization of LaCrO₃(s) and samples of the composition LaCrO₃+ La₂O₃ was investigated in the temperature range of 1887-2333 K by Knudsen effusion mass spectrometry using Knudsen cells made of tungsten lined completely with iridium. The species Cr(g), CrO(g ), CrO₂(g), and LaO(g) were identified in the vapor. Their partial pressures were determined by calibration with pure platinum solid. The thermodynamic activity of Cr₂O₃, a _cr2o₃ in LaCrO₃ for the Cr₂0₃-poor phase boundary of this phase was In a_Cr2o₃⁼ -(17953/T) - 0.485 (temperature T given in K) for the temperature range of the measurements with a probable overall error of ± 13%. The following values and temperature dependence of ΔG°_f,T resulted for the formation of LaCrO₃(s) according to the reaction 0.5Cr₂O₃(s) + 0.5La₂O₃(s) → LaCrO₃(s): ΔG°_f,2100= -78.9 ± 1.1 kj/mol, Δ H°_f,298= -76.8 ± 5.2 kj/mol, and ΔG°_r(kJ/mol) = -74.7 - 0.00202 T . Computations for the vaporization of LaCrO₃ were conducted to show the volatility of this material in different atmospheres at high temperatures.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.     

Hydrothermal Synthesis and Formation Mechanisms of Lanthanum Tin Pyrochlore Oxide

Well-defined La₂Sn₂O₇ with a phase-pure pyrochlore structure was produced by hydrothermal synthesis at temperatures as low as 200°C. Production of phase-pure La₂Sn₂O₇ requires a pH above 10, and higher pH accelerates the crystallization process. The synthesis produced spherical particles of average particle size ∼0.59 μm (±0.12) and surface area ∼14.1 m²/g. SEM and TEM observation for morphologic evolution and kinetic analysis during crystallization indicated that La₂Sn₂O₇ formation probably proceeds via a two-step reaction. First a transient dissolution–precipitation occurs. Then the primary crystallites aggregate because of their colloidal instability, and heterocoagulation with the lanthanum hydrous oxide precursor particles also occurs. The sluggish reaction rate at the later stage of reaction is characterized by an in situ transformation, where the soluble tin species is diffused through the porous La₂Sn₂O₇ aggregates to react with entrapped lanthanum precursors.