Microstructure and Grain-Boundary Effect on Electrical Properties of Gadolinium-Doped Ceria

The microstructural evolution and grain-boundary influence on electrical properties of Ce_0.90Gd_0.10O_1.95 were studied. The nanoscale powders synthesized from a semibatch reactor exhibited 50% green density and 92% sintering density at 1200°C (∼200°C lower than previous studies). Impedance spectra as a function of temperature and grain size were analyzed. The Ce_0.90Gd_0.10O_1.95 with finest grain size possessed highest overall grain-boundary resistance; this contribution was eliminated at temperatures >600°C, regardless of grain size. The grain conductivity was independent of grain size and was dependent on temperature with two distinct regimes, indicative of the presence of Gd'_Ce− V _o^∘∘ complexes that dissociated at a critical temperature of ∼580°C. The activation energy for complex dissociation was ∼0.1 eV; the value for the grain-boundary was ∼1.2eV, which was size independent.     

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.     

Low-Temperature Synthesis of Praseodymium-Doped Ceria Nanopowders

Praseodymium-doped ceria (CeO₂) nanopowders have been synthesized via a simple but effective carbonate-coprecipitation method, using nitrates as the starting salts and ammonium carbonate as the precipitant. The precursors produced in this work are ammonium rare-earth double carbonates, with a general formula of (NH₄)_0.16Ce_{1− x} Pr _x (CO₃)_1.58·H₂O (0 < x ≤ 0.20), which directly yield oxide solid solutions on thermal decomposition at a very low temperature of ∼400°C. Praseodymium doping causes a gradual contraction of the CeO₂ lattice, because of the oxidation of Pr³⁺ to smaller Pr⁴⁺, and suppresses crystallite coarsening of the oxides during calcination. Dense ceramics have been fabricated from the thus-prepared nanopowders via pressureless sintering for 4 h at a low temperature of 1200°C.     

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.     

Filtration Behavior of Nanoparticulate Ceria Slurries

The influence of poly(acrylic acid) (PAA) concentration and molecular weight on the filtration behavior of CeO₂ slurries with 20 nm particle size was studied. Low-viscosity suspensions could be produced by adsorbing a monolayer of PAA that covered the nanoparticles. For all suspensions investigated, the cake permeability was lower than predicted by the Kozeny–Carman equation and decreased with increased filtration pressure because of the presence of a compressible PAA layer 3–5 nm thick on the surface of the particles. The permeability of the nanoparticulate cakes decreased with increased polymer addition because of clogging.     

Interface Structure of an Epitaxial Cubic Ceria Film on Cubic Zirconia

A cubic CeO₂ (001) film with a thickness of ∼58 nm was grown epitaxially on Y₂O₃-stablized cubic ZrO₂ by oxygen-plasma-assisted molecular-beam epitaxy (OPA-MBE). The interface was characterized using high-resolution transmission electron microscopy (HRTEM). The interface exhibited coherent regions separated by equally spaced misfit dislocations. When imaged from the [100] direction, the dislocation spacing is 3.3 ± 0.5 nm, which is slightly shorter than the expected value of 4.9 nm calculated from the differences in lattice constants given in the literature, but is fairly consistent with that of 3.9 nm which was calculated using the lattice mismatch measured by electron diffraction. Thus, the results presented here indicate that the lattice mismatch between the film and the substrate is accommodated mainly by interface misfit dislocations above some critical thickness.     

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.     

Electrochemical Stability of Strontium-Doped Ceria Electrolyte in Solid-Oxide Fuel Cell Applications

SrO-doped CeO₂ electrolyte has been evaluated in single-cell configuration under solid-oxide fuel cell operating conditions. Because of oxygen loss from the crystal lattice, the material experiences a macroscopic expansion of several percent at 1000°C. On extended cell operation, strontium precipitates-out at/near the anode, resulting in irreversible cell degradation in the case of SrO-doped CeO₂. Precipitation and diffusion of SrO causes decreased ionic conductivity and may result in anode delamination. SrO precipitation is attributed to insolubility of the dopant in the reduced CeO₂ phase. The diffusion of strontium seems to be related to the flux of oxygen through the sample, but an exact mechanism is unknown.     

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.     

Preparation and Spherical Agglomeration of Crystalline Cerium(IV) Oxide Nanoparticles by Thermal Hydrolysis

Crystalline cerium(IV) oxide nanoparticles with a cubic fluorite structure could be synthesized from cerium(IV) ammonium nitrate solutions with a relatively high concentration of cerium(IV) (such as 0.5 mol/dm³) via thermal hydrolysis at 150°–240°C. The effects of the treatment temperature, the salt concentration, and the addition of sulfate ions on the crystallite size and morphology of the synthesized particles were investigated. The crystalline nanoparticles had a tendency to agglomerate and form spherical secondary particles with the addition of either ammonium sulfate or sulfuric acid. The existence of sulfate ions in the acidified solution was confirmed to be a factor of consequence for spherical agglomeration of the nanoparticles.     

Raman Spectroscopy of Nanocrystalline Ceria and Zirconia Thin Films

The results of Raman-scattering studies of nanocrystalline CeO₂ and ZrO₂:16% Y (YSZ) thin films are presented. The relationship between the lattice disorder and the form of the Raman spectra is discussed and correlated with the microstructure. It is shown that the Raman line shape results from phonon confinement and spatial correlation effects and yields information about the material nonstoichiometry level.     

Preliminary Experiments of In Situ Atomic Force Microscopy Observation of Hydroxyapatite Formation on Bioactive Glass Surface

This paper demonstrates the use of atomic force microscopy (AFM) to image the bioactivity of phosphate glasses that are well-known to react rapidly in simulated body fluid. The present study demonstrates that the hydroxyapatite (HAP) crystalline layer found via AFM in the examined samples coincides with that identified using scanning electron microscopy. Moreover, the effect of a notorious bacteriostatic cation—tetravalent cerium, Ce(IV)—on the kinetics of the HAP layer is investigated in CeO₂-doped bioactive glasses.     

In Situ Observations of Phase Transition Using High-Temperature Neutron and Synchrotron X-ray Powder Diffractometry

It is of vital importance for the study of phase diagrams to investigate in situ diffusionless phase transition points at high temperatures. We have developed high-temperature techniques to measure in situ neutron and synchrotron X-ray powder diffractometry profiles. This paper reviews our recent studies obtained using these methods. The new furnace for high-temperature neutron diffraction study yields no extra peaks caused by heaters and refractory; thus, we have been able to measure very small neutron signals from the sample. Quality neutron diffraction data at high temperatures up to ∼1590°C have been analyzed using the Rietveld method for various materials, such as zirconia solid solutions and calcium titanate. High-resolution synchrotron X-ray diffractometry enables exact determination of the phase transition temperatures of perovskite-related materials.     

Hydrothermal Synthesis of Xenotime-Type Gadolinium Orthophosphate

Xenotime-type GdPO₄ (tetragonal, I 4₁/ amd ) has been synthesized hydrothermally at 400°C. X-ray powder data have been presented, and the lattice parameters have been calculated as a = 0.6969(2) nm and c = 0.6095(3) nm.     

Synthesis of Cerium α-SiAlON with Nuclei Addition

Cerium α-SiAlON ceramics were made from a powder mixture of Si₃N₄-AlN-CeO₂ that contained 1 wt% yttrium α-SiAlON powder. Plasma-activated sintering was used to examine the effect of the cooling rate on the formation of α-SiAlON. The formation of cerium α-SiAlON was suggested to be controlled by the nucleation at the surface of α-SiAlON nuclei, because α-phase formation could not occur without the addition of SiAlON powder. The solubility of cerium in the α-SiAlON was shown to be less than a previously predicted critical value.     

Electrical Conductivities of (CeO2)1−x(Y2O3)x Thin Films

Electrical properties of CeO₂ thin films of different Y₂O₃ dopant concentration as prepared earlier were studied using impedance spectroscopy. The ionic conductivities of the films were found to be dominated by grain boundaries of high conductivity as compared with that of the bulk ceramic of the same dopant concentration sintered at 1500°C. The film grain-boundary conductivities were investigated with regard to grain size, grain-boundary impurity segregation, space charge at grain boundaries, and grain-boundary microstructures. Because of the large grain boundary and surface area in thin films, the impurity concentration is insufficient to form a continuous highly resistive Si-rich glassy phase at grain boundaries, such that the resistivity associated with space-charge layers becomes important. The grain-boundary resistance may originate from oxygen-vacancy-trapping near grain boundaries from space-charge layers. High-resolution transmission electron microscopy coupled with a trans-boundary profile of electron energy loss spectroscopy gives strong credence to the space-charged layers. Since the conductivities of the films were observed to be independent of crystallographic texture, the interface misorientation contribution to the grain-boundary resistance is considered to be negligible with respect to those of the impurity layer and space-charge layers.     

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.     

Production and optical properties of Ce3+-activated and Lu3+-stabilized transparent gadolinium aluminate garnet ceramics

We first report the novel Ce³⁺-activated and Lu³⁺-stabilized gadolinium aluminate garnet (GAG) transparent ceramics derived from their precipitation precursors via a facile co-precipitation strategy using ammonium hydrogen carbonate (AHC) as the precipitant. The resulting precursors in liquid phase were substantially homogeneous solid solutions and could directly convert into sinterable garnet powders via pyrolysis. Substituting 35 at.% of Lu³⁺ for Gd³⁺ was effective to stabilize the cubic GAG garnet structure and transparent (Gd,Lu)₃Al₅O₁₂:Ce ceramics were successfully fabricated by vacuum sintering at 1715°C. The ceramic transparency was improved by optimizing the particle processing conditions and the best sample had an in-line transmittance of ~70% at 580 nm (Ce³⁺ emission center) and over 80% in partial infrared region with a fine average grain size of ~4.5 μm. Transparent (Gd,Lu)₃Al₅O₁₂:Ce ceramics have a short critical wavelength (<200 nm) and a maximal infrared cut-off at ~6.6 μm. Both the (Gd,Lu)₃Al₅O₁₂:Ce phosphor powder and the transparent ceramic exhibited characteristic yellow emission of Ce³⁺ with strong broad emission bands from 490 to 750 nm upon UV excitation into two groups of broad bands around 340 and 470 nm. The photoluminescence and photoluminescence excitation intensities as well as the quantum yield were greatly enhanced via high-temperature densification. Both the phosphor powder and ceramic bulk had short effective fluorescence lifetimes.     

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.