Toward nanograined gadolinia doped ceria via two-step sintering at ultralow temperature and its electrical conductivity

Highly dense (>98%) and nanograined (∼60 nm) gadolinia doped ceria are obtained from ultrafine powders by adopting two-step sintering (TSS) procedure at an ultralow temperature of 750 °C with a dwell time of 20 h, which is the lowest sintering temperature for ceria family without sintering aids up to now. Electrochemical impedance spectroscopy investigations suggest that the electrical conductivities of densified electrolytes are closely related to sintering temperature and grain size, and GDC900-750 exhibits the highest total electrical conductivity of 3.640 S m⁻¹ at 700 °C in air. Fitting calculation indicates partial grain-size dependence of oxygen vacancy association enthalpy and grain-size independence of oxygen ion migration enthalpy. Grain boundary maturity influences on grain boundary conductivity to some extent, and younger grain boundary endues the densified electrolytes with higher grain boundary conductivity.     

Effect of Sm and Gd dopants on structural characteristics and ionic conductivity of ceria

Sm- and Gd-doped ceria electrolytes Ce_0.9Gd_0.1O_1.95 (GDC) and Ce_0.9Sm_0.1O_1.95 (SDC) were prepared by using the Pechini method. The microstructural and physical properties of the samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry/differential thermal analysis (TG/DTA) and Fourier Transform Infrared Spectroscopy (FTIR). The TG/DTA and XRD results indicated that a single-phase fluorite structure formed at a relatively low calcination temperature, 400 °C. The XRD patterns of the samples revealed that the crystallization of the SDC powders was superior than that of the GDC powders at 400 °C. The sintering behavior and ionic conductivity of the GDC and SDC pellets were also investigated. The sintering results showed that the SDC samples were found to have higher sinterability than the GDC samples at a relatively low sintering temperature, 1300 °C, a significantly lower temperature than 1650 °C, which is required for ceria solid electrolytes prepared by solid state techniques. The impedance spectroscopy results revealed that SDC has a higher ionic conductivity compared to GDC.     

Fabrication and Characterization of Ce0.8Sm0.2O1.9 Microtubular Dual-Structured Electrolyte Membranes for Application in Solid Oxide Fuel Cell Technology

Samaria-doped ceria (SDC, Ce_0.8Sm_0.2O_1.9) ceramic powders of submicrometer size were synthesized by a sol–gel auto-combustion method. From these powders microtubes with a dual structure comprising of a dense layer and a porous substrate layer were fabricated in a single step through a phase inversion/sintering technique. A sintering temperature in excess of 1450°C is required for SDC to achieve gastight microtubes. The mechanical strength of the SDC microtubes increases with increasing sintering temperature and may attain up to 208 MPa when sintered at 1500°C. Electrical impedance spectroscopy studies indicate that the SDC microtubes have electrical conductivities of 4.46 × 10⁻⁴–0.072 S/cm and corresponding activation energy of 81.9 kJ/mol at temperatures between 400° and 800°C. Full fuel cells were fabricated by coating Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) on to the inner surface and a Ni-SDC cermet on to the outer surface of the gastight microtubes to act as the cathode and the anode, respectively. The resultant BSCF|SDC|Ni-SDC microcells have a stable output maximum of 106 mW/cm² at 750°C when hydrogen and air were used as fuel and oxidant gas, respectively.     

Ionic conductivity and relaxations of In-doped GDC (gadolinium doped ceria) ceramics

The effect of In doping on the sintering behaviors and electrical properties of Gd_0.1Ce_0.9O_1.95 (Gd-doped ceria, or GDC) was investigated. The solubility limit of In in GDC was determined to be ~2 at%, and the lattice parameter of GDC was found to decrease from 5.417(7) Å to 5.416(5) Å with 2 at% In dopant. The mean grain size of the sintered body decreased with increasing In content. The concentration of In did not significantly affect the conductivity of the samples; however, undoped GDC showed the highest conductivity. Cole-Cole plots showed that the activation energies of the grain boundaries and grain interiors decreased and increased, respectively, as the In concentration increased to 1 at%. The decreased grain-boundary activation energy is attributed to the segregation of the negatively charged dopant at the grain boundaries, while the increased activation energy of the grain interiors is attributed to the decreases in both the lattice parameters and binding energies with In doping.     

Polyol Synthesis and Investigation of Ce1−xRExO2−x/2 (RE = Sm,Gd, Nd,La, 0 ≤ x ≤ 0.25) Electrolytes for IT‐SOFCs

In this study, we aimed to examine the effect of dopant type and concentration on the ionic conductivity of ceria‐based electrolytes. Ceria electrolytes doped with samarium (SDC), gadolinium (GDC), neodymium (NDC), and lanthanum (LDC) for solid oxide fuel cells were prepared through the polyol process. Acetate compounds of cerium and dopants were used as starting materials, and triethylene glycol was used as a solvent. Prepared powders and pellets were characterized by TG/DTA, XRD, FTIR, SEM, EIS, and EDS techniques. The results of the TG/DTA and XRD indicated that a single‐phase fluorite structure formed at the relatively low calcination temperature of 500°C. The relative densities of the pellets were higher than 90% and these finding were supported by the SEM images. The lattice parameters of the samples increased with the dopant concentration. According to the electrochemical analysis results, the samples with maximum conductivity values were SDC‐20, GDC‐15, NDC‐15, and LDC‐15. The results of the impedance spectroscopy revealed that the SDC‐20 sample exhibited the highest ionic conductivity with a value of 4.29 × 10^?2 S/cm at 800°C in air.     

Grain size effect on the electrical properties of nanocrystalline ceria

The total and partial electronic conductivities of gadolinium doped ceria (Ce_0.95Gd_0.1O_1.95−δ: GDC) with nanometer grain size have been evaluated in an attempt to identify the nanosize effect in heavily doped ceria. Nanocrystalline GDC bulk specimens with relatively high densities (≥96% of theoretical density) and various grain sizes (70, 100, 170 nm) were successfully fabricated by a conventional solid-state sintering method. According to the measurements of total and partial electronic conductivity via AC-impedance and DC polarization methods, respectively, no significant grain size dependence appeared for either type of conductivity. Furthermore, both total and partial electronic conductivity were not significantly different from those of microcrystalline GDC, which indicated that, upon nanostructuring within the examined grain size range, nanostructured bulk GDC was not affected by any nanosize effect: either space charge layer effect or grain boundary blocking effect.     

Preparation and Characterization of Samaria-Doped Ceria Electrolyte Materials for Solid Oxide Fuel Cells

The microstructure, thermal expansion, mechanical property, and ionic conductivity of samaria-doped ceria (SDC) prepared by coprecipitation were investigated in this paper. The results revealed that the average particle size ranged from 10.9±0.4 to 13.5±0.5 nm, crystallite dimension varied from 8.6±0.3 to 10.7±0.4 nm, and the specific surface area distribution ranged from 62.6±1.8 to 76.7±2.2 m²/g for SDC powders prepared by coprecipitation. The dependence of lattice parameter, a, versus dopant concentration, x , of Sm³⁺ ion shows that these solid solutions obey Vegard's rule as a ( x )=5.4089+0.10743 x for Ce_{1− x} Sm _x O_{2−1/2 x} . For SDC ceramics sintered at 1500°C for 5 h, the bulk density was over 95% of the theoretical density; the maximum ionic conductivity, σ_800°C=(22.3±1.14) × 10⁻³ S/cm with minimum activation energy, E _a=0.89±0.02 eV, was found in the Ce_0.80Sm_0.20O_1.90 ceramic. A dense Ce_0.8Sm_0.2O_1.9 ceramic with a grain size distribution of 0.5–4 μm can be obtained by controlling the soaking time at 1500°C. When the soaking time was increased, the microhardness of Ce_0.8Sm_0.2O_1.9 ceramic increased, the toughness slightly decreased, which was related to grain growth with the soaking time.     

Electrical properties of samaria-doped ceria electrolytes from highly active powders

The correlations of the microstructures and the electrical properties of high reactive Ce_0.8Sm_0.2O_1.9 (SDC) powders, synthesized via an optimal carbonate coprecipitation method, were investigated. Microstructure of the SDC ceramics sintered at 900-1400 °C showed uniform grain and small grain size, compared with those prepared with various methods under similar sintering conditions. These features may be related to high conductivity (σ_600 °C = 0.022 S cm⁻¹) and low activation energy for conduction (0.66 eV). AC impedance spectra were involved to resolve grain interior and grain boundary resistance. Grain boundary contribution to the total resistance showed the values below 1/2 at 200-450 °C, suggesting low grain boundary effect. The motion enthalpy for the grain interior conduction decreased while the association enthalpy increased with sintering temperature up to 1300 °C, which might be possibly originated from the increase in lattice parameters with the sintering temperature.     

Synthesis of nano-crystalline Gd0.1Ce0.9O2−x for IT-SOFC by aerosol flame deposition

Nano-sized gadolinia-doped ceria (GDC) can be used as an IT-SOFC electrolyte, oxygen gas sensor or abrasives. In this study, nano-sized GDC powders with bimodal particle distribution of about 10 nm and 200 nm particle size were successfully synthesized by aerosol flame deposition (AFD). The resulting effects of sintering temperature on microstructure and electrical properties were investigated in the sintering temperature range 1100–1400 °C. The pellet had a completely dense microstructure after sintering at 1400 °C for 10 h. Raman measurement showed an increase of oxygen vacancy due to shift between reduced and oxidized states (Ce³⁺ ↔ Ce⁴⁺) with increasing sintering temperature. The formation of oxygen vacancies noticeably increased the ionic conductivity above 1300 °C.     

Direct addition of lithium and cobalt precursors to Ce0.8Gd0.2O1.95 electrolytes to improve microstructural and electrochemical properties in IT-SOFC at lower sintering temperature

To improve the microstructural and electrochemical properties of gadolinium-doped ceria (GDC) electrolytes, materials co-doped with 0.5–2?mol% of lithium and cobalt oxides were successfully prepared in a one-step sol gel combustion synthesis route. Vegard's slope theory was used to predict the dopant solubility and the sintering behaviour. The charge and size of the added dopant influence the atom flux near the grain boundary with a change in the lattice parameter. In fact, compared to traditional multi grinding steps, sol gel combustion facilitates molecular mixing of the precursors and substitution of the dopant cations into the fluorite structure, considerably reducing the sintering temperature. Adding precursors of lithium and cobalt, as dopant, increases the GDC densification and reduces its traditional sintering temperature down to 1000–1100?°C, with an improvement of electrochemical properties. Impedance analysis showed that the addition of 2?mol% of lithium or 0.5?mol% of cobalt enhances the conductivity with a consequent improvement of cell performances. High total conductivities of 1.26·10^?1 S?cm^?1 and 8.72·10^?2 S?cm^?1 at 800?°C were achieved after sintering at 1000?°C and 1100?°C for ²LiGDC and ^0.5CoGDC, respectively.     

Enhanced Oxygen Reduction Reaction in Nanocrystalline Surface of Samaria‐Doped Ceria via Randomly Distributed Dopants

The randomly distributed dopant effects in nanocrystalline samaria‐doped ceria (SDC) interlayers were investigated by systematically varying the dopant distributions and grain‐boundary densities via post‐annealing process. Electrochemical analysis demonstrates that films having lower annealing or fabrication temperatures exhibit superior surface oxygen kinetics, particularly in the case of oxygen reduction reactions (ORRs). Further investigation through TEM‐EELS shows that the typical segregation of dopants is not significantly present in SDC film deposited via the RF sputtering method, while post‐annealed SDC film shows strong dopant accumulation near the grain boundary. The results indicate that the randomly distributed dopants, in addition to the nano grains, may further enhance surface reactions by providing more preferential reaction sites due to a higher content of defects at the interface.     

Effect of Gallia Addition on the Sintering Behavior of Samaria-Doped Ceria

Samaria-doped ceria (SDC) was prepared by using the solid-state reaction method. Sintering of SDC was significantly promoted by adding a small amount of gallium. SDC that had 1% of gallium added, sintered at 1450°C, showed almost the same properties as SDC sintered at 1600°C. Measurements showed that the addition of gallia could reduce the sintering temperature by 150°C without deteriorating the properties of SDC as an electrolyte for solid oxide fuel cells.     

Effects of Prior Annealing on the Spark Plasma Sintering of Nanostructured Y2O3 Powders

The effects produced by annealing Y₂O₃ nanopowders on their spark plasma sintering (SPS) behavior are systematically investigated in this work. It is found that the annealed powders display higher sinterability with respect to the as‐received ones. Indeed, the maximum densification level reached from pristine powders is about 97.5%, whereas density decreases when further increasing either the sintering temperature or the dwell time. In contrast, the density of SPS products obtained from pretreated powder monotonically increases with temperature and processing time, thus leading to fully dense materials in 30 min at 1050°C and 60 MPa. Correspondingly, it is found that the annealing treatment markedly inhibits grain coarsening during SPS. Thus, dense translucent samples with grain size below 100 nm can be attained from annealed powders. On the other hand, white‐opaque specimens with significantly coarser microstructures (up to 1‐μm‐sized grains) are obtained when pristine powders are directly processed under the same sintering conditions. Furthermore, it is observed that the annealing treatment of SPS samples in air allows for graphite contamination removal, whereas no improvement in term of light transmittance is produced.     

Tape Casting, Pressureless Sintering, and Grain Growth in Ti3SiC2 Compacts

In this work we demonstrate that fine Ti₃SiC₂ powders can be tape-cast and/or cold-pressed and pressureless-sintered in Ar- or Si-rich atmospheres to produce fully dense, oriented microstructures in which the basal planes are parallel to the surfaces. Carbon- and/or Si-rich environments suppress grain growth. In the case of the tape casting, the C-residue from binder burnout results in small core grains relative to the surface grains that can grow significantly. When sintering in high Si activities, titanium silicide phases form at the grain boundaries that slow grain growth. Annealing the latter in Ar at 1600°C, for extended periods (30 h), rids the samples of these grain-boundary phases, which in turn results in grain growth. The advantage of the latter process is that the final grain size distribution is more uniform from surface to bulk.     

Ultrafast high-temperature sintering of gadolinia-doped ceria

Ultrafast high-temperature sintering (UHS) is a rapidly growing research area of material science and engineering. Herein we present UHS of gadolinia-doped ceria (GDC) powders in single and multi-step approaches. The sintered ceramics were characterized from a physical and electrochemical point of view. When the power is applied gradually during the multistep UHS process crack-free GDC ceramics can be obtained with 95 % bulk density using commercial powder. Oxalate converted GDC powder gave 86 % bulk density with the same multistep sintering process. Additionally, it is shown that multistep UHS is also suitable for multilayer co-sintering necessary for solid oxide fuel cells (SOFC), as demonstrated by the production of dense GDC electrolyte in tight contact with porous electrodes.     

Effects of Yttrium on the Sintering and Microstructure of Alumina–Silicon Carbide "Nanocomposites"

Alumina and alumina-based "nanocomposites" with 2 and 5 vol% silicon carbide and varying amounts of yttria (0–1.5 wt%) have been prepared by pressureless sintering in the temperature range 1450°–1650°C. The effects of composition and sintering temperature on density and microstructure are reported. Yttria inhibited sintering in alumina, but enhanced the sinterability of the nanocomposites. It also induced abnormal grain growth in both alumina and nanocomposites, but strongly bimodal grain size distributions could be prevented by careful choice of the composition and the sintering temperature. Fully dense (>99%), fine-grained alumina–5 vol% SiC–1.5 wt% yttria nanocomposites were produced from uniaxially pressed powders with a yttria content of 1.5 wt% and a sintering temperature of 1600°C. Reasons for this behavior are discussed, and it is suggested that the enhancement of sintering in the alumina–SiC materials is because of the reaction of silica on the surface of the silicon carbide particles with alumina, yttria, and possibly magnesia, modifying the grain boundary composition, resulting in enhanced grain boundary diffusion. scanning transmission electron microscopy/energy-dispersive X-ray data show that such co-segregation does occur in the yttria-containing nanocomposites.     

Sintering of surfactant modified ZnO–Bi2O3 based varistor nanopowders

Surfactant modified nano-origin ZnO–Bi₂O₃ varistor powder was prepared in presence of cetyltrimethyl ammonium bromide (CTAB) surfactant through an aqueous reflux reaction at 100 °C. The compacted varistor discs made from the nano-origin powders were subjected to step-sintering, microwave sintering and solid-state sintering. The influences of CTAB in different sintering methods were analyzed from the densification characteristics, evolution of sintered microstructures and associated varistor properties (I–V). The conventional solid-state sintering produced 96% theoretical sintered dense samples at 1100 °C. The step and microwave sintered samples showed 93% and 99% sintered densities, respectively, with controlled microstructures having grain sizes in the range of 2–6 μm at the given conditions. The CTAB advantages were clearly seen in grain structuring and grain boundary properties, in addition to the enhanced densification and homogenous microstructures for obtaining high breakdown voltage and non-linearity coefficient.     

Synthesis and Processing Characteristics of Ba0.65Sr0.35TiO3 Powders from Catecholate Precursors

Powders of composition Ba_0.65Sr_0.35TiO₃ were prepared from catecholate precursor phases, BaTi(C₆H₄O₂)₃ and SrTi (C₆H₄O₂)₃. The physical and chemical properties of the base powders, and those doped with 0.2 wt% manganese, are reported in detail. The dimensions of the primary particles in the starting powders were of the order of 20–50 nm, but the occurrence of abnormal grain growth during sintering promoted grain sizes in the ceramic of up to ∼100 μm. In some microstructures, coarse grains coexisted with a ∼1-μm fraction to produce a characteristic bimodal grain size distribution. By contrast, under comparable sintering conditions, namely 1350° or 1400°C for 1 h, grain growth in Mn-doped samples was suppressed, leading to uniform microstructures with a grain size of only a few micrometers. The pellet densities were nevertheless similar, 97% of theoretical in both doped and undoped samples. No significant difference was observed in the dielectric permittivity of the two compositions: the peak relative permittivity occurred at ∼20°C, with a maximum value of ∼22 000.     

Microstructure and Electrical Properties of Sc2O3-Doped, Rare-Earth-Oxide-Doped, and Undoped BaTiO3

Polycrystalline BaTiO₃ prepared from alkoxy-derived high-purity submicron powders was studied. Highly dense bodies with uniform grain size were obtained typically by uniaxial cold-pressing at 3000 psi and isostatic pressing at 30,000 psi followed by sintering at 1300° to 1350°C in air for 0.5 to 1 h. Using the same consolidation parameters and intimate mixing of residual concentrations of highly active fine-particulate rare-earth oxides to act as grain-growth inhibitors, nearly theoretically dense bodies with a uniform microstructure and 1 to 1.5 μm grain size were obtained. Typical microstructures with well-defined 90° and 180° domain patterns characteristic of BaTiO₃: were observed. Also, an example of a checkerboard pattern resulting from a 〈111〉 ingrown twin plane in the structure which is independent of the Curie temperature was found. Electrical measurements on the undoped material indicated room-temperature dielectric constant and tan δ values of 5000±500 and 4×10⁻³, respectively. Very high k values and dissipation factors were observed with the La₂O₃- and Nd₂O₃-doped samples.     

Effect of Oxygen Partial Pressure on the Dielectric Properties and Microstructures of Cofired Base-Metal-Electrode Multilayer Ceramic Capacitors

The dielectric properties, dopant distributions, and microstructures of BaTiO₃-based multilayer ceramic capacitors (MLCCs) sintered in H₂–N₂–H₂O atmospheres with     =10^−7.5 Pa (BMX-7.5) and     =10^−9.5 Pa (BMX-9.5) were studied, and the effects of oxygen partial pressures were analyzed. Dielectric measurements showed that BMX-7.5 had a lower dielectric constant at temperatures above 20°C, but a higher dielectric constant at temperatures below 10°C when compared with BMX-9.5. The coexistence of core–shell and core grains was observed in bright field (BF) transmission electron microscopy images in both types of capacitors. Triple-point and grain boundary phases were observed more frequently in BMX-9.5 than in BMX-7.5, and energy-dispersive X-ray spectrometer point-by-point analysis revealed that these second phases contained high concentrations of dopants such as Si, Y, and Ca. The dopant concentration in the shell regions in BMX-7.5 was higher than that in similar regions in BMX-9.5. Smeared and twisted grain boundaries with fringes observed in both types of MLCCs indicated that the shell regions in both samples were formed either by diffusion of foreign ions into BaTiO₃ or by crystallization of grain boundary and triple-point liquid phases. It was deduced that the partial pressure of oxygen in the sintering atmosphere influenced the microstructures, dopant distributions, and core–shell ratios of the grains in these materials.