Reactive Ceria Nanopowders via Carbonate Precipitation

Nanocrystalline CeO₂ powders have been successfully synthesized via a carbonate precipitation method, using ammonium carbonate (AC) as the precipitant and cerium nitrate hexahydrate as the cerium source. The AC/Ce³⁺ molar ratio ( R ) affects significantly precursor properties, and spherical nanoparticles can be produced only in a narrow range of 2 < R ≤ 3. The precursor, having an approximate composition of Ce(OH)CO₃·2.5H₂O, decomposes to CeO₂ at temperatures ≥300°C. The CeO₂ powder calcined at 700°C exhibits high reactivity and can be densified to >99% of theoretical at 1000°C.     

Phase-Selective Pyrolysis and Pr3+ Luminescence in a YF3–Y2O3 System from a Single-Source Precursor

Pr³⁺-doped YF₃ (orthorhombic), YO_0.80F_1.40 (orthorhombic), YOF (rhombohedral), and Y₂O₃ (cubic) films were synthesized on quartz-glass substrates through pyrolysis of a single-source trifluoroacetate precursor at temperatures between 400° and 900°C in air. Phase-selective deposition was achieved by controlling heating temperature and time. YF₃, which formed first from the precursor, was transformed to YO_0.80F_1.40, YOF, and Y₂O₃. Photoluminescent properties of Pr³⁺-doped films were examined using ultraviolet excitation. An intense green photoluminescence was observed in the YOF:Pr³⁺ film, which was deposited at 700°C, through an efficient charge transfer (O²⁻–Pr³⁺) excitation.     

Synthesis of Ultrafine Ceria Powders by Mechanochemical Processing

The synthesis of ultrafine cerium dioxide (CeO₂) powders via mechanochemical reaction and subsequent calcination was studied. Anhydrous CeCl₃ and NaOH powders, along with NaCl diluent, were mechanically milled. A solid-state displacement reaction—CeCl₃+ 3NaOH → Ce(OH)₃+ 3NaCl—was induced during milling in a steady-state manner. Calcination of the as-milled powder in air at 500°C resulted in the formation of CeO₂ nanoparticles in the NaCl matrix. A simple washing process to remove the NaCl yielded CeO₂ particles ∼10 nm in size. The particle size was controlled in the range of ∼10–500 nm by changing the calcination temperature.     

Effect of the Presence of Ammonium Peroxodisulfate on the Direct Precipitation of Ceria and Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

Direct precipitation of nanometer-sized particles of ceria–zirconia (CeO₂–ZrO₂) solid solutions with cubic and tetragonal structures was successfully attained from acidic aqueous solutions of cerium(III) nitrate (Ce(NO₃)₃) and zirconium oxychloride (ZrOCl₂) through the addition of ammonium peroxodisulfate ((NH₄)₂S₂O₈), because of promotion of the hydrolysis via the oxidation of Ce³⁺ ions, together with the simultaneous hydrolysis of ZrOCl₂ under hydrothermal conditions. Ultrafine CeO₂ particles also could be formed from relatively concentrated aqueous solutions of the same trivalent cerium salt in the presence of (NH₄)₂S₂O₈ via hydrolysis. The crystallite size and lattice strain of as-precipitated solid solutions varied, depending on the composition within the CeO₂–ZrO₂ system. Creation of a solid solution of ZrO₂ into a fluorite-type CeO₂ lattice clearly introduced lattice strain, as a consequence of the decreasing crystallite size. Both the direct precipitation process and the effectiveness of the presence of (NH₄)₂S₂O₈ for the synthesis of CeO₂–ZrO₂ solid solutions were discussed.     

Optimization of Praseodymium-Doped Cerium Pigment Synthesis Temperature

The development of red pigments is of great interest to the ceramic industry. Pr(IV) stabilization in a CeO₂ matrix yields materials with a red color. In this study, the traditional ceramic method involving solid-state reaction was used to prepare pigments in the system Ce_{1− x} Pr _x O_2−δ (0.005 ≤ x ≤ 0.1) from mixtures of rare-earth oxides. The chemical stability of these pigments was then determined in some industrial glazes. The glazing tests indicate that the powder samples calcined at 1200° and1300°C are unstable, whereas those calcined at 1400° and 1500°C are stable. These findings are related to the nonformation of a solid solution, to which the pigmenting power is attributed, in calcinations at temperatures below 1400°C.     

Oxygen Storage Capacity, Specific Surface Area, and Pore-Size Distribution of Ceria–Zirconia Solid Solutions Directly Formed by Thermal Hydrolysis

The oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solutions that were directly formed as nanocrystals by thermal hydrolysis of acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ at 150°C increased from 94 μmol of O₂/g for pure CeO₂ to >400 μmol of O₂/g for compositions of CeO₂/ZrO₂ with molar ratios (C/Z) from 74.1/25.9 to 41.7/58.3 (maximum value of 431 μmol O₂/g was reached at the composition C/Z = 51.7/48.3) and then decreased with increased ZrO₂ content in the solid solutions. As compared with pure CeO₂, the CeO₂–ZrO₂ solid solutions that contained <84.8 mol% ZrO₂ maintained high specific surface area and large pore volume with nanosized pores (pore size at maximum pore volume) <10 nm in diameter after heat treatment at 700°C.     

Microstructure and Photoluminescence Properties of Mg-Doped BaTiO3:Pr3+ Phosphor

The photoluminescence of Mg-doped BaTiO₃:Pr³⁺ (Pr³⁺: 0.1 mol%) ceramics was investigated by changing the doping concentration of Mg and the sintering temperature. The results indicated that the intensity of red emission due to the ¹ D ₂→³ H ₄ transition of Pr³⁺ exhibited significant dependence on both the Mg doping content and the sintering temperature; the strongest red emission intensity was observed for 2.0 mol% Mg-doped ceramics sintered at 1050°C. An interpretation of the results obtained was made in terms of the changes in the crystal structure and microstructure of the ceramics.     

Negative Thermal Expansion in (HfMg)(WO4)3

A single-phase material (HfMg)(WO₄)₃ with an orthorhombic structure, A₂ (WO₄)₃-type tungstate, has been successfully prepared for the first time by the calcination of HfO₂, MgO, and WO₃, substituting Hf⁴⁺ and Mg²⁺ for A³⁺ cations in A₂(WO₄)₃. The new material shows a negative thermal expansion coefficient of approximately −2 ppm/°C from room temperature to 800°C. The mechanism of negative thermal expansion is assumed to be the same as that of Sc₂(WO₄)₃.     

Photoluminescence of Cerium-Doped α-SiAlON Materials

Cerium-doped α-SiAlON (M _x Si_{12−( m + n )}Al _{m + n} O _n N_{16– n} ) materials have been prepared by gas-pressure sintering and post-hot-isostatic-press (HIP) annealing, using four powder mixtures of α-Si₃N₄, AlN, and either (i) CeO₂, (ii) CeO₂+ Y-α-SiAlON seed, (iii) CeO₂+ Y₂O₃, or (iv) CeO₂+ CaO. Cerium-containing CeAl(Si_{6– z} Al _z )(N_{10– z} O _z ) (JEM) phase, rather than Ce-α-SiAlON phase, forms in the sample with only CeO₂, whereas a single-phase α-SiAlON generates in samples with dual doping (CeO₂+ Y₂O₃ and CeO₂+ CaO). On ultraviolet-light excitation, JEM gives one broad emission band with maximum at 465 nm and a shoulder at 498 nm; α-SiAlON shows an intense and broad emission band that peaks at 500 nm. The unusual long-wavelength emissions in JEM and α-SiAlON are due to increases in the nephelauxetic effect and the ligand-field splitting of the 5 d band, because the coordination of Ce³⁺ in JEM and α-SiAlON is nitrogen enriched.     

Phase Relations and Thermal Expansion Studies in the Ceria–Yttria System

The synthesis, characterization, and bulk and lattice thermal expansions of a series of compounds with general composition Ce_{1– x} Y _x O_{2– x /2} (0.0 ≤ x ≤ 1.0) are reported. The XRD pattern of each product was refined to learn the solid solubility limit and the homogeneity range. The solid solubility limit of YO_1.5 in CeO₂ lattice, under the conditions of slow cooling from 1400°C, is represented as Ce_0.55Y_0.45O_1.775 (i.e., 45 mol% of YO_1.5). The subsequent compositions were biphase. There was no solubility of CeO₂ into the lattice of YO_1.5. The bulk thermal expansion measurements from ambient to 1123 K, as investigated using a dilatometer, revealed that the α_l (293–1123 K) values, within the homogeneity range, decreased on increased Y³⁺ content. A similar trend was observed for average lattice thermal expansion coefficient, α_a (293–1473 K), as investigated using high-temperature XRD. No ordered phases were obtained in this system under the used conditions. These studies on Ce_{1– x} Y _x O_{2– x /2} (0.0 ≤ x ≤ 1.0) system can be used to simulate the phase relation and thermal expansion behavior of Pu_{1– x} Y _x O_{2– x /2} (0.0 ≤ x ≤ 1.0), because CeO₂ is widely used as a surrogate material for PuO₂.     

Raman Spectra of Rare-Earth Phosphate Glasses

Raman spectra have been recorded for glasses in the binary systems CeO₂-P₂O₅ and Pr₂O₃-P₂O₅. The cerium phosphate glasses were prepared having different concentrations of CeO₂ and the praseodymium phosphate glasses with different ratios of Pr³⁺ to Pr⁴⁺. The spectra indicate that both cerium and praseodymium enter the glass in modifying sites. We see no changes in the Raman spectra with Pr³⁺/Pr⁴⁺ ratio. Measurements of the density and glass transition temperature are also reported.     

Sc2O3 Nanopowders via Hydroxyl Precipitation: Effects of Sulfate Ions on Powder Properties

Hydroxyl-type Sc₂O₃ precursors have been synthesized via precipitation at 80°C with hexamethylenetetramine as the precipitant. The effects of starting salts (scandium nitrate and sulfate) on powder properties are investigated. Characterizations of the powders are achieved by elemental analysis, X-ray diffractometry (XRD), differential thermal analysis/thermogravimetry (DTA/TG), high-resolution scanning electron microscopy (HRSEM), and Brunauer-Emmett-Teller (BET) analysis. Hard-aggregated precursors (γ-ScOOH·0.6H₂O) are formed with scandium nitrate, which convert to Sc₂O₃ at temperatures ≥400°C, yielding nanocrystalline oxides of low surface area. The use of sulfate leads to a loosely agglomerated basic sulfate powder having an approximate composition of Sc(OH)_2.6(SO₄)_0.2·H₂O. The powder transforms to Sc₂O₃ via dehydroxylization and desulfurization at temperatures up to 1000°C. Well-dispersed Sc₂O₃ nanopowders (∼64.3 nm) of high purity have been obtained by calcining the basic sulfate at 1000°C for 4 h. The effects of SO₄²⁻ on powder properties are discussed.     

CeO2−CoO Phase Diagram

Phase equilibria in the CeO₂−CoO system at temperatures above 1500°C were investigated. The microstructures and the phase compositions of the DTA (differential thermal analysis) samples and the quenched solid pellets were analyzed using SEM (scanning electron microscope), EDX (energy dispersive X-ray), and WDX (wavelength dispersive X-ray). A eutectic reaction was found at 1645 ± 5°C. The eutectic point was calculated to be at 82 ± 1.5 mol% CoO. The eutectic phases were the CeO₂-rich phase (containing <5 mol% CoO) and the CoO-rich phase (containing ∼0.5 mol% CeO₂). At 1580°C, the solubility of CoO in CeO₂ was ∼3 mol%.     

Effect of V2O5 Doping on the Sintering and Dielectric Properties of M-Phase Li1+x−yNb1−x−3yTix+4yO3 Ceramics

The effect of the addition of V₂O₅ on the structure, sintering and dielectric properties of M -phase (Li_{1+ x − y} Nb_{1− x −3 y} Ti _x +4 _y )O₃ ceramics has been investigated. Homogeneous substitution of V⁵⁺ for Nb⁵⁺ was obtained in LiNb_{0.6(1− x )}V_{0.6 x} Ti_0.5O₃ for x ≤ 0.02. The addition of V₂O₅ led to a large reduction in the sintering temperature and samples with x = 0.02 could be fully densified at 900°C. The substitution of vanadia had a relatively minor adverse effect on the microwave dielectric properties of the M -phase system and the x = 0.02 ceramics had [alt epsilon]_r= 66, Q × f = 3800 at 5.6 GHz, and τ_f= 11 ppm/°C. Preliminary investigations suggest that silver metallization does not diffuse into the V₂O₅-doped M -phase ceramics at 900°C, making these materials potential candidates for low-temperature cofired ceramic (LTCC) applications.     

Pr3+/Er3+ Codoped Ge-As-Ga-S Glasses as Dual-Wavelength Fiber-optic Amplifiers for 1.31 and 1.55 μm Windows

Fluorescence emissions at both 1.31 and 1.55 μm communication windows were observed from Pr³⁺/Er³⁺ codoped Ge-As-Ga-S glasses with a single wavelength pumping at 986 nm. The lifetime of the Er³⁺:⁴ I _11/2 level decreased as the Pr³⁺ concentration increased, and that of the Pr³⁺:¹ G ₄ level increased as the Er³⁺ concentration increased. Energy transfer from the Er³⁺:⁴ I _11/2 level to the Pr³⁺:¹ G ₄ level was responsible for emission of the 1.31 μm fluorescence from the Pr³⁺:¹ G ₄ level. Ge-As-Ga-S glasses that have been doped with Pr³⁺ and Er³⁺ cations are promising amplifier materials for both 1.31 and 1.55 μm communication windows.     

Fiber Strength Retention of Lanthanum- and Cerium Monazite-Coated Nextel™ 720

Nextel™ 720 fibers were coated with LaPO₄ and CePO₄ monazite. The coatings were applied using washed and unwashed rhabdophane sols derived from La(NO₃)₃/(NH₄)₂HPO₄ and a washed sol derived from Ce(NO₃)₃/H₃PO₄. The coatings were cured in-line at 900°–1300°C. Multiple coatings were also applied. Fiber strength was retained after coating with washed sols, but not with unwashed sols. These results are consistent with earlier work on LaPO₄ monazite fiber coatings derived from La(NO₃)₃/H₃PO₄.     

Properties and Performance of Cation-Doped Ceria Electrolyte Materials in Solid Oxide Fuel Cell Applications

Cation-doped CeO₂ electrolyte has been evaluated in single-cell and short-stack tests in solid oxide fuel cell environments and applications. These results, along with conductivity measurements, indicate that an ionic transference number of ∼0.75 can be expected at 800°C. Single cells have shown a power density >350 mW/cm². Multicell stacks have demonstrated a peak performance of >100 mW/cm² at 700°C using metallic separators.     

Wet-Chemical Routes Leading to Scandia Nanopowders

Two wet-chemical routes have been used to synthesize Sc₂O₃ nanopowders from nitrate solutions employing ammonia water (AW) and ammonium hydrogen carbonate (AHC) as the precipitants. The precursors and the resultant oxides are characterized by elemental analysis, X-ray diffractometry, differential thermal analysis/thermogravimetry, high-resolution scanning electron microscopy, and Brunauer-Emmett-Teller analysis. Crystalline γ-ScOOH· n H₂O ( n ≈ 0.5) is the only phase obtained by the AW method. This phase dehydrates to Sc₂O₃ at ∼400°C, yielding hard aggregated nanocrystalline Sc₂O₃ powders. Three types of precursors have been synthesized by the AHC method, depending on the AHC/Sc³⁺ molar ratio ( R ): amorphous basic carbonate [Sc(OH)CO₃·H₂O] at R ≤ 3, crystalline double carbonate [(NH₄)Sc(CO₃)₂·H₂O] at R ≥ 4, and a mixture of the two phases at 3 < R < 4. Among these precursors, only the basic carbonate shows spherical particle morphology, ultrafine particle size (∼50 nm), and weak agglomeration. Sc₂O₃ nanopowders (∼28 nm) with high surface area (∼49 m²/g) have been prepared by calcining the basic carbonate at 700°C for 2 h.     

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.     

Blocking Grain Boundaries in Yttria-Doped and Undoped Ceria Ceramics of High Purity

CeO₂ samples doped with 10, 1.0, and 0.1 mol% Y₂O₃ and undoped CeO₂ samples of high purity were studied by impedance spectroscopy at temperatures <800°C and under various oxygen partial pressures. According to microstructural investigations by SEM and analytical STEM (equipped with EDXS), the grain boundaries were free of any second phase, providing direct grain-to-grain contacts. An amorphous siliceous phase was detected at only a few triple junctions, if at all; as a result, its contribution to the grain-boundary resistance was negligible. Nevertheless, the specific grain-boundary conductivities were still 2–7 orders of magnitude lower than the bulk conductivities, depending on dopant concentration, temperature, and oxygen partial pressure. The charge carrier transport across the grain boundaries occurred only through the grain-to-grain contacts, whose properties were then determined by the space-charge layer. The space-charge potential in acceptor-doped CeO₂ was positive, causing the simultaneous depletion of oxygen vacancies and accumulation of electrons in the space-charge layer. The very low grain-boundary conductivities can be accounted for by the oxygen-vacancy depletion; the accumulation of electrons became evident in weakly doped and undoped CeO₂ at high temperatures and under low oxygen partial pressures.