Phase diagram calculations of ZrO2-based ceramics with an emphasis on the reduction/oxidation equilibria of cerium ions in the ZrO2-YO1.5-CeO2-CeO1.5 system

Phase diagram calculations that were made previously for the ZrO₂-MO _m/2 (m = 2, 3, 4) systems and for the ZrO₂-YO_1.5-MO _m/2 (M = transition metals) systems have been extended to the ZrO₂-YO_1.5-CeO₂(-CeO_1.5) system to make an attempt to explain (1) thermogravimetric (TG) results as a function of oxygen potential, (2) electronic conductivity as a function of oxygen potential, and (3) a miscibility gap observed in air. The interaction parameters for the CeO₂-CeO_1.5-YO_1.5 system were obtained from the reported oxygen nonstoichiometry in CeO_2−x and rate earth doped ceria, (Ce,RE)O_2−δ . The interaction parameters for the ZrO₂-CeO₂ subsystem were obtained so as to reproduce the observed miscibility gap at 1273 K. Those thermodynamic properties can reproduce consistently the experimental behaviors of the electronic conductivity and the TG results in the (Zr_1−x Ce _x )_0.8Y_0.2O_1.9 solid solutions; these indicate the enhancement of reduction of CeO₂.     

Opportunities for TBCs in the ZrO2-YO1.5-TaO2.5 system

An examination of the ZrO₂-YO_1.5-TaO_2.5 system reveals several promising attributes for use in thermal barrier coating applications. The rather unique presence of a stable, non-transformable tetragonal region in this ternary oxide system allows for phase stability to high temperatures (1500 °C). Selected compositions with high levels of yttria and tantala have also shown superior resistance to vanadate corrosion than the commercially utilized 7YSZ. In addition, Y + Ta stabilized zirconia compositions within the non-transformable tetragonal phase field exhibit toughness values comparable or somewhat higher than those of 7YSZ, which bodes well for their durability as TBCs. These promising attributes are discussed in this paper in the context of recent experimental work.     

Preparation of nanometric CeO2–ZrO2–Nd2O3 solid solution and its catalytic performances

A kind of nanometric CeO₂–ZrO₂–Nd₂O₃ (CZN) solid solution for a carrier in the automotive three-way catalysts was synthesized by a coprecipitation method and characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption–desorption (BET), scanning electron microscopy (SEM) and oxygen storage capacity (OSC). For the purpose of comparison, an unincorporated CeO₂–ZrO₂ (CZ) was also synthesized. The XRD measurements disclose the prepared CeO₂–ZrO₂–Nd₂O₃ have a face-centered cubic fluorite structure and nanoparticle sizes. According to the results of XPS, Nd³⁺ ions can enter the CZ lattice and form a homogenous solid solution. Oxygen storage capacity measurements reveal that CeO₂–ZrO₂–Nd₂O₃ display high oxygen mobility at a low temperature. The results of the activity tests show that the catalyst exhibits good three-way catalytic activity and fairly wide range of air-to-fuel ratios.     

Composition, surface structure, and thermal behavior of ZrO2 + TiO2/Ti and ZrO2 + CeOx + TiO2 composites formed by plasma-electrolytic oxidation

Specific surface structures of ZrO₂ + TiO₂ (I) and ZrO₂ +CeO_x + TiO₂ (II) coatings on titanium before and after annealing at 850°C for 24 h in air are studied. Whiskers are found on the surface of type-I coatings before annealing, and perfectly edged crystals composed of TiO₂ and ZrO₂ oxides are found upon annealing. Pores in both coatings have a multilevel structure. In the case of type-I coatings, orifices of pores are covered with titanium. In type-II coatings, pore orifices contain titanium, zirconium, and oxygen. Oxygen deficiency implies that titanium and zirconium are present in pore orifices in metallic state. In type-II coatings, the surface distribution of cerium is heterogeneous. Mechanical treatment of the annealed coatings causes their exfoliation from the substrate metal. In the case of both coatings, the exfoliating surfaces are composed of TiO₂ blocks containing excess oxygen.     

Thermal behavior of the amorphous precursors of the ZrO2–GaO1.5 system

The amorphous precursors of the ZrO₂–GaO_1.5 system on the ZrO₂-rich side of the concentration range were prepared by co-precipitation from aqueous solutions of the corresponding salts. Thermal behavior of the amorphous precursors was monitored using differential thermal analysis (DTA), X-ray powder diffraction (XRD), Raman spectroscopy and field emission scanning electron microscopy (FE-SEM). Crystallization temperature of the amorphous precursors rose with an increase in the GaO_1.5 content, from 405 °C (0 mol% GaO_1.5) to 720 °C (50 mol% GaO_1.5). The results of Rietveld refinements indicated that the maximum solubility of Ga³⁺ ions in the ZrO₂ lattice (43 mol%) occurred in the metastable products obtained after crystallization of the amorphous precursors. Further thermal treatment caused a decrease of the solubility limits, which became negligible after calcination at 1100 °C. The results of Raman spectroscopy showed that the incorporation of Ga³⁺ ions partially stabilized the tetragonal polymorph of ZrO₂, but could not stabilize its cubic polymorph. The incorporation of Ga³⁺ ions caused a linear decrease in the unit-cell volume of the ZrO₂-type solid solutions, but the rate of the decrease turned out to be smaller than the rate obtained after the incorporation of bigger Fe³⁺ ions.     

Elastic behavior of La0.67Ca0.33MnO3:ZrO2 composites

A series of Colossal Magneto Resistance materials, with compositional formula (1 − x) La_0.67Ca_0.33MnO₃ + xZrO₂ (where x = 0%, 10%, 20%, 40%, 60%, 80%) were prepared by sol–gel technique. When characterized structurally by X-ray diffraction they are found to have cubic structure. After measuring their bulk densities, the ultra sonic longitudinal (V_l) and shear velocities (V_s) were measured at room temperature using the pulse transmission technique. Using the ultrasonic data, the values of Young's and rigidity moduli along with Poisson's ratio and Debye temperatures have been calculated. As the materials are porous, zero porous elastic moduli have also been arrived at using a well-known model. The observed variation of elastic moduli with varying ZrO₂ concentration has been explained qualitatively.     

Multiphase magnetic state of Ca1 ? x La x MnO3 ? δ single crystals ( x = 0.03, 0.05, 0.07) containing oxygen vacancies

Magnetic properties (magnetization, dynamic and static susceptibility) and transport properties (resistance and magnetoresistance) have been studied in a temperature range of 2–600 K in magnetic fields to 90 kOe for single crystals of Ca_{1 − x} La _x MnO_{3 − δ} with a weak electron doping (x ≤ 0.07) grown in argon and oxygen atmospheres. The magnetic state of Ca_{1 − x} La _x MnO_{3 − δ} single crystals is multiphase. Below T = T _N(G) ∼ 110 K, in all the crystals there coexists an AFM G phase with an FM contribution and an AFM C phase. In crystals with x = 0.07, a transition from the paramagnetic phase into the AFM C phase occurs in part of their volume below T ∼ 130–150 K. In crystals with x = 0.05 annealed in oxygen, an anomaly of paramagnetic susceptibility is observed near T ^* ∼ 270 K, which is related to the formation of FM clusters near defects. At x = 0.05 and 0.07, AFM correlations are retained in the paramagnetic state (to 600 K). The differences in the magnetic and transport properties of single crystals grown in argon and oxygen are explained by the various content of oxygen vacancies and by their possible ordering. Original Russian Text ? N.N. Loshkareva, A.V. Korolev, T.I. Arbuzova, N.I. Solin, A.M. Balbashov, N.V. Kostromitina, 2007, published in Fizika Metallov i Metallovedenie, 2007, Vol. 103, No. 3, pp. 261–270.     

Thermal and mechanical properties of ZrO2-CeO2 plasma-sprayed coatings

The thermal and mechanical properties of ZrC₂-C_{eO 2}plasma-sprayed coatings were evaluated to examine their potential as a thermal barrier coating. ZrO₂-CeO₂ solid-solution powders containing up to 70 mol % CeO₂ are successfully plasma sprayed, but cerium content decreases during spraying due to the vaporization of cerium oxide. Hardness is greatest at 30 mol% CeO₂. With increased CeO₂ content, the thermal conductivity decreases to 0.5 W/m K and the thermal expansion coefficient increases to 12.5 x 10_-6 /K. Increased torch input power causes both the relative density and the hardness to increase monotonically, while the thermal conductivity and the thermal expansion coefficient are not significantly affected. When heated above 1300 K, the coating shrinks considerably due to sintering and its thermal conductivity increases abruptly.     

Investigation on Oxygen Chemical Diffusion Properties of Perovskite Oxides (La1?x Pr x )0.6Sr0.4Co0.8Fe0.2O3?δ

Perovskite oxide samples of (La_1−x Pr _x )_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (x = 0.2, 0.4, 0.6, 0.8) are obtained by solid-state reaction method. The oxygen chemical diffusion properties of (La_1−x Pr _x )_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ are determined by electrical conductivity relaxation technique. The results show that the conductivity of (La_1−x Pr _x )_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ increases with the increase of oxygen partial pressure. The (La_1−x Pr _x )_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ samples have a high oxygen chemical diffusion coefficient, which decreases linearly with a decrease in temperature and an increase in Pr content. The oxygen chemical diffusion coefficient D _chem remains fairly constant at high PO₂. The oxygen chemical diffusion coefficient is the highest for (La_1−x Pr _x )_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ with x = 0.2, and attains a value of 9.41 × 10⁻⁵ cm² s⁻¹ at 600 °C. This shows the material’s promise as a cathode material for intermediate temperature solid oxide fuel cells.     

Impact of Ce ion on microstructure and luminescence character of Ho/Yb co-doped ZrO2 nanocrystal

By solid-state synthesis method, Ho³⁺/Yb³⁺ co-doped CeO₂-ZrO₂ nano-powders have been prepared. The concentration of Ce⁴⁺ ions has greater effect to the oxygen lattice structure. When the concentration of Ce⁴⁺ ions is 30 mol%, the oxygen lattice is a tetrahedral space group and the luminescence intensity of the sample is strongest. The results show that the lattice structure can be changed by inducting the Ce⁴⁺ ions into Ho³⁺/Yb³⁺ co-doped ZrO₂. And the emission character can be improved.     

Effects of Sc doping on electrical conductivity of BaZrO<Subscript>3</Subscript> protonic conductors

BaZr1-xScxO3-0.5x (x=0.07,0.10,0.13,0.16) powders were prepared by solid-state reaction method,and ZnO was used as sintering aid.Samples with different amount of ZnO additive were sintered at 1450 ℃ for 6 h in air.Single cubic perovskite phase proton conductors were obtained.Conductivity was measured by electrochemical workstation.It was shown that Sc doping could increase conductivity through enhancing the carrier concentration in the material,but excessive Sc content might decrease the carrier concentration because of its charge compensation.ZnO had an influence on carrier concentration and mobility and affected the electrical conductivity.2 mol％ ZnO and 13 mol％ ScO1.5 doped sample showed the highest DC conductivity of 3.6 × 10-3 S·cm-1 tested at 800 ℃ in wet hydrogen atmosphere.     

Thermodynamic study of CVD–ZrO2 phase diagrams

Chemical vapor deposition (CVD) of zirconium oxide (ZrO₂) from zirconium acetylacetonate Zr(acac)₄ has been thermodynamically investigated using the Gibbs’ free energy minimization method and the FACTSAGE program. Thermodynamic data Cp°, ΔH° and S° for Zr(acac)₄ have been estimated using the Meghreblian–Crawford–Parr and Benson methods because they are not available in the literature. The effect of deposition parameters, such as temperature and pressure, on the extension of the region where pure ZrO₂ can be deposited was analyzed. The results are presented as calculated CVD stability diagrams. The phase diagrams showed two zones, one of them corresponds to pure monoclinic phase of ZrO₂ and the other one corresponds to a mix of monoclinic phase of ZrO₂ and graphite carbon.     

Ablation behavior of ZrB2–SiC–ZrO2 ceramic composites by means of the oxyacetylene torch

Ablation behavior of ZrB₂–SiC–ZrO₂ ceramics with two ZrO₂ contents was investigated using oxyacetylene torch. Thermogravimetric analysis demonstrated that ceramic with 10 vol% ZrO₂ showed initial weight change at higher temperature than the one with 20 vol% ZrO₂. After same ablation condition, lighter oxidized microstructure and lower weight loss and line gain were obtained from ceramic with 10 vol% ZrO₂. Ablation mechanism revealed that excessive ZrO₂ would supply much path to the inward transport of oxygen, which led to the dissatisfactory resistance to oxidation and ablation for the ceramic with 20 vol% ZrO₂.     

Synthesis and characterization of new pyrochlore solid solution Bi1.5Sb1.5Cu1−xMnxO7

A new pyrochlore solid solution with formula Bi_1.5Sb_1.5Cu_1−xMn_xO₇ has been synthesized using ceramic method at 1000 °C. The cell parameter decreases linearly with increasing manganese concentration. Rietveld refinements for (B_1.5Mn_0.5)(Sb_1.5Mn_0.5)O₇ compound using X-ray powder diffraction data confirmed an overall A₂B₂O₇ cubic pyrochlore structure with a = 10.42749 (4) Å and Fd-3m symmetry. The reliability factors are R_wp = 3.48%; R_p = 2.37%; R_exp = 1.65% and R_Bragg = 1.58%. The magnetic susceptibility measurements achieved between 4 and 300 K indicate a paramagnetic behaviour with an oxidation state “2+” of the manganese ion. The electric resistance measured using complex impedance spectroscopy method put in evidence a decrease of the electric resistance with the temperature, which reached 5 × 10² Ω at 675 K. Dielectric properties depend on the variation of frequency and temperature, results indicate a conductive compound.     

Tie-lines and mixing properties of solid solutions in the system CaO-SrO-PbO-O at 1100 K

Phase relations in the system CaO-SrO-PbO-O₂ at 1100 K have been determined by equilibrating samples with different compositions in air, oxygen, or evacuated ampoules for 7 days and characterizing quenched specimens by optical and scanning electron microscopy, energy-dispersive analysis of x-rays (EDX), and x-ray diffraction (XRD). There is a solid-state miscibility gap in the pseudo-binary system CaO-SrO, and continuous solid solubility between Ca₂PbO₄ and Sr₂PbO₄ at 1100 K. Substitution of Ca for Sr occurs only to a limited extent (∼2 mol.%) in SrPbO₃. The calcium-rich solid solutions (Ca_1−y Sr _y )₂PbO₄ characterized by y≤0.255 are in equilibrium with PbO in air; compositions with y≥0.255 coexist with (Ca_1−z Sr _z )PbO₃. There is a three-phase region involving the two monoxide solid solutions (Ca_1−x Sr _x )O on either side of the miscibility gap with x=0.24 and 0.71 and (Ca_1−y Sr _y )₂PbO₄ with y=0.96. Accurately determined are the locations of tie-lines between the solid solutions. Attainment of equilibrium was checked by the conventional tie-line rotation technique. The excess Gibbs energy of mixing of the solid solution with orthorhombic structure is obtained by an analysis of tie-line data; for the mixing of one mole of Ca and Sr represented by (Ca_1−y Sr _y )Pb_0.5O₂, ΔG ^E =y(1−y) [15,840−2950 y] J/mol. The thermodynamic properties suggest the onset of immiscibility in this solid solution below 884 (±5) K. The miscibility gap is asymmetric with a critical composition at y=0.43 (±0.02). Inside the triangle (Ca_1−y Sr _y )Pb_0.5O₂−(Ca_1−z Sr _z )PbO₃−PbO, a small liquid-phase region is present close to the PbO corner, surrounded by three two-phase fields. Each corner of the approximately triangular liquid-phase region is associated with a three-phase field.     

Tie-lines and mixing properties of solid solutions in the system CaO-SrO-PbO-O at 1100 K

Phase relations in the system CaO-SrO-PbO-O₂ at 1100 K have been determined by equilibrating samples with different compositions in air, oxygen, or evacuated ampoules for 7 days and characterizing quenched specimens by optical and scanning electron microscopy, energy-dispersive analysis of x-rays (EDX), and x-ray diffraction (XRD). There is a solid-state miscibility gap in the pseudo-binary system CaO-SrO, and continuous solid solubility between Ca₂PbO₄ and Sr₂PbO₄ at 1100 K. Substitution of Ca for Sr occurs only to a limited extent (∼2 mol.%) in SrPbO₃. The calcium-rich solid solutions (Ca_1−y Sr _y )₂PbO₄ characterized by y≤0.255 are in equilibrium with PbO in air; compositions with y≥0.255 coexist with (Ca_1−z Sr _z )PbO₃. There is a three-phase region involving the two monoxide solid solutions (Ca_1−x Sr _x )O on either side of the miscibility gap with x=0.24 and 0.71 and (Ca_1−y Sr _y )₂PbO₄ with y=0.96. Accurately determined are the locations of tie-lines between the solid solutions. Attainment of equilibrium was checked by the conventional tie-line rotation technique. The excess Gibbs energy of mixing of the solid solution with orthorhombic structure is obtained by an analysis of tie-line data; for the mixing of one mole of Ca and Sr represented by (Ca_1−y Sr _y )Pb_0.5O₂, ΔG ^E =y(1−y) [15,840−2950 y] J/mol. The thermodynamic properties suggest the onset of immiscibility in this solid solution below 884 (±5) K. The miscibility gap is asymmetric with a critical composition at y=0.43 (±0.02). Inside the triangle (Ca_1−y Sr _y )Pb_0.5O₂−(Ca_1−z Sr _z )PbO₃−PbO, a small liquid-phase region is present close to the PbO corner, surrounded by three two-phase fields. Each corner of the approximately triangular liquid-phase region is associated with a three-phase field.     

Thermodynamic optimization of the Na2O-B2O3 pseudo-binary system

The Na₂O-B₂O₃ system is thermodynamically optimized by means of the CALPHAD method. A two-sublattice ionic solution model, (Na⁺¹)_P(O⁻²,BO₃ ⁻³,B₄O₇ ⁻²,B₃O_4.5)_Q, has been used to describe the liquid phase. All the solid phases were treated as stoichiometric compounds. A set of thermodynamic parameters, which can reproduce most experimental data of both phase diagram and thermodynamic properties, was obtained. Comparisons between the calculated results and experimental data are presented.     

Au/ZrO2 catalysts for low-temperature water gas shift reaction: Influence of particle sizes

The size effects of Au and ZrO₂ particles on the structural property and the catalytic performance of Au/ZrO₂ catalysts for the water gas shift reaction were extensively investigated. It was found that the Au-ZrO₂ contact boundaries played essential roles in determining the catalytic reactivity. By keeping the size of Au particle to be ∼3 nm, the increase in the particle size of ZrO₂ from ∼7 nm to ∼55 nm caused significant decrease in the reaction rate. When the particle size of ZrO₂ was fixed at ∼20 nm, the conversion of CO decreased greatly with increasing the size of gold particle from 2.9 to 6.2 nm. IR spectroscopy and kinetic study revealed that the water gas shift reaction occurred at the Au-ZrO₂ contact boundaries, where CO is adsorbed on the Au species and H₂O is activated on the surface of ZrO₂ through the formation of formate species, acting as key reaction intermediates.