Nanostructured cerium oxide: preparation and properties of weakly-agglomerated powders

Nanocrystalline powders of cerium oxide were prepared from cerium(III) nitrate solution by a two-stage precipitation process which yielded weakly-agglomerated powders with a crystallite size smaller than 5 nm. Hydrogen peroxide was added to cerium nitrate at 5°C to slowly oxidise Ce³⁺ to Ce⁴⁺ and thereby initiate homogeneous precipitation with the formation of dense spherical agglomerates. The precipitation process was completed by the addition of ammonium hydroxide which disrupted the spherical agglomerates leaving a weakly-agglomerated power of hydrated ceria. The process was completed by hydrothermal treatment at 180°C without increase in crystallite size. The powders were characterised by X-ray diffraction, transmission electron microscopy and thermogravimetric analysis. The weakly-agglomerated state of the powder and the uniform crystallite size of under 5 nm are favourable characteristics for many applications.     

Structures and electrical conductivities of Gd3+ and Fe3+ co-doped cerium oxide electrolytes sintered at low temperature for ILT-SOFCs

Gd³⁺ and Fe³⁺ co-doped cerium oxide electrolytes, Ce_0.9Gd_0.1‐xFe_xO_2-δ (x?=?0.00, 0.01, 0.03, 0.05, 0.07, 0.10), were prepared by co-precipitation for ultrafine precursor powders and sintering for densified ceramic pellets. The crystal and microscopic structures were characterized by XRD, FESEM and Raman spectroscopy and their electrical properties were studied by AC impedance spectroscopy and the measurement of single cell's outputs. In comparison with Ce_0.9Gd_0.1O_1.95, the ceramic pellets of Ce_0.9Gd_0.1‐xFe_xO_2-δ with a relative density of 95% can be obtained after sintered at 1000?°C for 5?h, showing a remarkably enhanced sintering performance with a sintering temperature reduction of 500?°C, which might be ascribed to the highly activated migration of constituent species in the cerium oxide lattice doped with Gd³⁺ and Fe³⁺ions. Moreover, the electrical conductivity of Ce_0.9Gd_0.1‐xFe_xO_2-δ can be significantly enhanced depending on the mole fraction x, with Ce_0.9Gd_0.07Fe_0.03O_1.95 exhibiting the highest electrical conductivity of 38 mS/cm at 800?°C, about 36% higher than that of Ce_0.9Gd_0.1O_1.95 electrolyte sintered at 1500?°C for 5?h. So, The Gd³⁺ and Fe³⁺ co-doped cerium oxide would be an excellent candidate electrolyte for ILT SOFCs due to its prominent sintering performance and enhanced electrical conductivity.     

Samarium doped ceria (SDC) synthesized by a metal triethanolamine complex decomposition method: Characterization and an ionic conductivity study

Samarium doped ceria (SDC) powders as solid electrolyte ceramics were successfully prepared via thermal decomposition of metal organic complexes containing triethanolamine (TEA) as a ligand. The SDC powders synthesized using various samarium doping contents were characterized by X-ray diffractometry, scanning electron microscopy, X-ray absorption spectroscopy, energy dispersive X-ray spectroscopy and Brunauer-Emmett-Teller (BET) analysis. The influences of samarium doping and the calcination temperature on the characteristics of the SDC materials were thoroughly investigated. An appropriate temperature for SDC powder calcination was identified by thermogravimetric analysis to be 600 °C. After sintering the calcined SDC powders at 1500 °C to obtain highly dense ceramic pellets, the electrical conductivity of the materials was examined by impedance spectroscopy. The influence of percentage of Sm³⁺ dopants in SDC materials on the observed conductivity were explained by correlating with the detailed analysis of the local structure and environment of Sm³⁺ within the SDC materials by using X-ray absorption spectroscopy. The conductivities of the SDC products reported in this work indicate that they are promising candidates for solid electrolytes in solid oxide fuel cell applications.     

Fabrication and characterisation of boron doped barium stabilised bismuth cobalt oxide nanocrystalline ceramic composite

Abstract

In this paper, the fabrication and characterisation processes of both boron doped and undoped barium stabilised bismuth cobalt oxide nanocrystalline ceramic powders using polymeric precursor were reported. Obtained boron doped barium stabilised bismuth cobalt oxide nanocrystalline ceramic powders, which have been synthesised by polymeric precursor technique at temperatures below 900°C and at atmospheric condition, were characterised by X-ray diffraction, Fourier transform infrared and scanning electron microscopy techniques. According to X-ray results, fcc and bcc phases coexist in the samples of the nanocrystalline ceramic powders. Crystallite sizes for body centred cubic structure were calculated using Scherrer equation for both boron doped and undoped samples. In addition, lattice parameters were calculated for all samples.     

Novel iron-rich mullite solid solution synthesis using fused-silica and α-Al2O3 powders

An iron-rich mullite solid solution was synthesized by using α-Al₂O₃, fused-silica and Fe₂O₃ powders at elevated temperatures. The phase compositions and microstructures of the synthesized samples were characterized by X-ray diffraction (XRD), energy dispersive spectrometer (EDS) and field emission scanning electron microscope (FESEM). The occurrence states of Fe²⁺ and Fe³⁺ at different temperatures were analysed by X-ray photoelectron spectroscopy (XPS). The influence and the reaction mechanism of Fe₂O₃ addition on the synthesis of the mullite solid solution were clarified. The results showed that with the addition of Fe₂O₃, a liquid-solid sintered state was formed at 1300–1400?°C, which leaded to a reduction in the mullitization temperature. After sintering at 1600?°C, the quantitative analysis showed that the mullite phase content was 100%. Meanwhile, the Fe^3+/2+ ions entered completely into the mullite to form a stable solid solution, which exhibited the crystal morphology of a spherical shape and a short columnar shape with a low aspect ratio. The crystal grains were interwoven and squeezed each other, showing good structural stability. The refractoriness under load (RUL) property of the sample sintered at 1700?°C was slightly higher than that of the sample sintered at 1600?°C.     

Intragranular nanocomposite powders as building blocks for ceramic nanocomposites

A powder-based bottom-up processing scheme is introduced for the production of ceramic nanocomposites. Internal displacement reactions between solid solution powders and metallic reactants proceeding via gaseous intermediates are utilized to generate nanostructured building blocks for the synthesis of ceramic nanocomposites. Subsequent rapid sintering results in ceramic nanocomposites, whose microstructures are inherited from the building blocks. This processing scheme is demonstrated for the production of titanium carbide nanocomposites featuring up to 28 wt.% intragranular tungsten inclusions derived from titanium-tungsten mixed carbide powders. Heat treatment of mixed carbide powders in evacuated ampoules containing titanium sponge and iodine at 1000°C for 24 h resulted in nanocomposite powders featuring tungsten precipitates within titanium carbide grains that were subsequently consolidated via spark plasma sintering at 1300°C for 10 min to produce titanium carbide/metallic tungsten nanocomposites. Transformation of mixed titanium–tungsten carbide powders to titanium carbide/metallic tungsten nanocomposite powders was analyzed via X-ray diffraction. Electron microscopy observations of microstructures pre- and post- sintering showed that the intragranular character of nanocomposite powders can be retained in sintered ceramic nanocomposites. The building block approach demonstrated in this work represents an improved method to make ceramic nanocomposites with majority intragranular character.     

Synthesis and characterisation of BaCeO3-based proton conductors obtained from freeze-dried precursors

A freeze-drying precursor method was used to obtain submicrometric powders of BaCeO₃ and BaCe_0.9Y_0.1O_3?δ proton conductors at temperatures as low as 800 °C. The phase formation and evolution with the temperature was studied by X-ray diffraction (XRD) and thermal analysis (TG-DTA). The microstructure of both powders and sintered pellets was examined by scanning electron microscopy (SEM). Dense ceramic materials were obtained at 1400 °C and the different contributions to the overall conductivity, bulk and grain boundary, were studied using impedance spectroscopy under different atmospheres.     

Surface modification of sintered magnesium oxide (MgO) with chromium oxide (Cr2O3) by pulsed laser irradiation in air and liquids

Surface modification of ceramic materials by laser irradiation is widely used as a non-contact, fast and thermally activated process to generate micro and nanostructures. The effects of liquids while surface modification by laser irradiation of ceramic materials under liquid environment are least explored so far. This study reports the effects of pulsed laser irradiation in air and liquids on the microstructure and morphologies of ceramic materials. Chromium oxide (Cr₂O₃) was mixed in different concentrations (3, 5 and 7% in weight) into magnesium oxide (MgO) matrix and was sintered at 1650 °C. The structure and morphology of the sintered ceramic pellets were characterized using X-ray diffraction and scanning electron microscopy. Presence of the spinel magnesium chromium oxide (MgCr₂O₄) was identified in these samples. For surface modification of these samples, laser irradiation is carried out in air and liquids (methanol, isopropyl alcohol and acetone) using 2 ns pulsed lasers (532 nm) of different pulse repetition rates and energies. The microstructure and morphologies of the samples after irradiation was analyzed and their crystalline structure and composition were maintained after laser irradiation. It was observed that the surface morphologies of the ceramic pellets were modified by laser irradiation as a combined effect of the medium (air/liquids), energy fluence and the concentration of the Cr₂O₃ in MgO. Our results show that pulsed laser irradiation especially in liquids is an effective technique for modifying surface morphology of ceramic materials.     

Synthesis and characterization of 10Sc1CeSZ powders prepared by a solid–liquid method for electrolyte-supported solid oxide fuel cells

10Sc1CeSZ is one of the most important electrolyte materials used for solid oxide fuel cells (SOFCs). A novel solid–liquid method (SLM) was adopted for the preparation of 10Sc1CeSZ nanopowder. High-purity, single-phase, homogeneous 10Sc1CeSZ powder was successfully prepared using this method. The resulting powders and ceramic pellets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). A cubic structure was obtained when the value of the specific surface area (SSA) of the starting material ZrO₂ was greater than 60 m² g⁻¹. A conductivity of 0.14 S cm⁻¹ at 800 °C was achieved for the sintered pellets. The performance of the electrolyte-supported cell (ESC) NiO+GDC/10Sc1CeSZ /10Sc1CeSZ +LSM reached 0.66 W cm⁻² at 0.75 V and 850 °C.     

Effect of heat treatment on the dispersion and sintering behaviour of tin doped indium oxide powders

Due to the importance of structural uniformity of ITO targets on the properties of ITO films, the untreated and heat treated tin doped indium oxide powders were used to study the effects of four different dispersants on the dispersion behaviour of nanosized ITO powders. The optimum dispersant is NH₄PAA and its optimum amount is 1.00?wt% when the pH value is 9.0. In addition, the effect of the treatment temperature of nanosized ITO powders on the dispersion and sintering behaviour was also studied by SEM, TEM and XRD. The solid loading of ITO slurries and the relative density of the sintered bodies prepared with ITO powders treated at 900?°C could reach 40?vol% (untreated, 25?vol%) and 98.53% (untreated, 95.04%), respectively. The results indicate that the heat treatment of powders at 900?°C allowed obtaining powders from which ITO aqueous suspensions with high solid loading could be prepared and dense bodies after sintering. In another word, the appropriate heat treatment process for tin doped indium oxide powders could reduce the sintering temperature by 50?℃ and refine the grain size.     

Effect of synthesis atmosphere on the proton conductivity of Y-doped barium zirconate solid electrolytes

Yttrium-doped barium zirconate ceramic powders were synthesized by the oxidant peroxide method in air and under controlled atmosphere of nitrogen inside a glove box. The powders were characterized by thermogravimetry, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. After uniaxial cold isostatic pressing, green pellets were sintered at 1600 °C for 4 h. The electrical conductivity behavior was accessed by electrochemical impedance spectroscopy. The results show that specimens synthesized under controlled atmosphere achieved higher electrical conductivity, two orders of magnitude higher than specimens prepared in laboratory air. The enhancement in electrochemical properties and increase in sintering ability is attributed to the less carbonate contamination as a result lower grain boundary density in the samples prepared under controlled atmosphere.     

Sinterability of Forsterite Prepared via Solid‐State Reaction

In this work, the sinterability of forsterite powder synthesized via solid‐state reaction was investigated. X‐ray diffraction (XRD) analyses indicate that the synthesized powder possessed peaks that correspond to stoichiometric forsterite. Scanning electron micrographs revealed that the powders were formed agglomerates, which were made up of loosely packed fine particles. Subsequently, the forsterite powders were cold isostatically pressed into a disk shape under 200 MPa and sintered in air at temperature ranging from 1200°C to 1500°C (interval of 50°C) with ramp rate of 10°C/min and dwelling time of 2 h. The sinterability of each sintered samples was examined in terms of phase stability, relative density, Vickers hardness, fracture toughness, and microstructural examination. XRD examination on all the sintered samples exhibited pure forsterite, in which the generated peaks were found to be in a good agreement with JCPDS card no. 34‐0189. The densification of forsterite progressed to reach a maximum relative density of ~91% at 1500°C. This study also revealed that high‐strength forsterite ceramic can be synthesized via solid‐state reaction as forsterite attained favorable mechanical properties, having fracture toughness of 4.88 MPam^1/2 and hardness of 7.11 GPa at 1400°C.     

Influence of dry- and wet-milled LLZTO particles on the sintered pellets

A Ta-doped Li₇La₃Zr₂O₁₂ (LLZTO) solid electrolyte is a promising candidate for all-solid-state lithium battery due to its high ionic conductivity and stability against lithium metal. In this work, physicochemical properties of both dry- and wet-milled LLZTO particles were investigated. Based on X-ray diffraction, Fourier transform–infrared, thermogravimetric analysis, and scanning electron microscopy results, it was confirmed that highly reactive LLZTO powder prepared in dry milling conditions exhibited faster size reduction, rougher surface morphology, fewer surface impurities, and less agglomerated particles, in contrast to those in wet milling conditions. Sintering these dry-milled powders at 1320°C for 10 min in the air via solid-state reaction produced dense ceramic pellets with a relative density of 97.4%. The room-temperature ionic conductivity for LLZTO pellet via the dry milling was determined to be 6.94 × 10⁻⁴ S cm⁻¹. Li–sulfur batteries based on the pellets showed an initial discharge capacity of 1301 mA h g⁻¹ and a coulombic efficiency of 99.82% when cycled at room temperature. The effect of the milled powder on the sintered pellets was discussed in terms of boundary mobility, pore mobility, and morphology.     

Influence of electric field strength on structure,microstructure, and electrical properties of flash sintered 8% mol Yttria-stabilized zirconia as a solid oxide fuel cell electrolyte

To study the effect of electric field on the characteristics of flash sintered materials, 8% mol. Yttria-stabilized zirconia (8YSZ) was isothermally flash sintered under various electric field strengths as a solid oxide fuel cell (SOFC) electrolyte. Structural, microstructural, and electrical characteristics were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Electrochemical impedance spectroscopy (EIS), respectively. Results show that the electric field did not affect the relative density of flash sintered 8YSZ. Electric fields stronger than 300 V cm^?1, however, transformed the cubic structure to tetragonal. Microstructural studies show that the average grain size of samples is independent of the applied electric field strength. Electrochemical impedance spectroscopy showed changes in the grain boundary characteristics upon using the electric field for flash sintering. Oxygen vacancy concentration in the grain boundary of flash sintered samples was more than ten times higher than conventionally sintered ones, which improved the conductivity in flash sintered samples.     

Calcia Stabilized Ceria Doped Zirconia Nanocrystalline Ceramic

Calcia-stabilized cerium doped cubic zirconia nanocrystalline ceramic was synthesized using poly (vinyl alcohol) as a polymeric precursor. Obtained ceramic was pressed into a cylindrical pellet and sintered at 850 °C. The calcined and sintered ceramics were characterized by XRF, XRD, BET and SEM. The XRD pattern of the calcined ceramic shows that the ceramic has a face centered cubic crystal structure. The SEM results show that the grain size of the ceramic was increased after sintering. The BET surface areas were determined as 13.236 and 4.397 m² g^?1 for the calcined and sintered ceramics, respectively.     

Optimization of a ScCeSZ/GDC bi-layer electrolyte fabrication process for intermediate temperature solid oxide fuel cells

Cost-effective wet ceramic coating techniques for fabricating ScCeSZ/GDC bi-layer electrolyte anode-supported button cells were investigated in this study. Aqueous ceramic slurries were prepared by ball milling and then used for Ni/ScCeSZ half cell fabrication by tape casting and spin coating. Prepared cells were tested at operating temperature between 700 and 800°C with a fuel composition of hydrogen:nitrogen 3:1 and air at the cathode. The cell with a spin coated GDC film showed the maximum power density of 1.142, 1.012, 0.813 W?cm^?2 at 800, 750, and 700°C, respectively. It was also able to produce power output around 0.7 W?cm^?2 for 500 h at 750°C, which confirms the cell operational stability. More importantly, the GDC film prepared by spin coating effectively avoided the formation of the (Zr,Ce)O₂^?based solid solution at the ceria/zirconia interface compared with the other cells with the co-casted and sintered GDC film.     

Electric field-assisted sintering anode-supported single solid oxide fuel cell

Cosintering (La_0.84Sr_0.16MnO₃ thin-film cathode/ZrO₂: 8 mol% Y₂O₃ thin-film solid electrolyte/55 vol.% ZrO₂:8 mol% Y₂O₃ + 45 vol.% NiO anode, ϕ = 12 × 1.5 mm thick pellet) was achieved by applying an electric field for 5 min at 1200°C. Impedance spectroscopy measurements of the anode-supported three-layer cell show an improvement of the electrical conductivity in comparison to that of a conventionally sintered cell. The scanning electron microscopy images of the cross-sections of electric field-assisted pressureless sintered cells show a fairly dense electrolyte and porous anode and cathode. Joule heating, resulting from the electric current due to the application of the AC electric field, is suggested as responsible for sintering. Dilatometric shrinkage curves, electric voltage and current profiles, impedance spectroscopy diagrams, and scanning electron microscopy micrographs show how anode-electrolyte-cathode ceramic cells can be cosintered at temperatures lower than the usually required.     

Flash sintering of a three‐phase alumina,spinel, and yttria‐stabilized zirconia composite

Three‐phase ceramic composites constituted from equal volume fractions of α‐Al₂O₃, MgAl₂O₄ spinel, and cubic 8 mol% Y₂O₃‐stabilized ZrO₂ (8YSZ) were flash‐sintered under the influence of DC electric fields. The temperature for the onset of rapid densification (flash sintering) was measured using a constant heating rate at fields of 50‐500 V/cm. The experiments were carried out by heating the furnace at a constant rate. Flash sintering occurred at a furnace temperature of 1350°C at a field of 100 V/cm, which dropped to 1150°C at a field of 500 V/cm. The sintered densities ranged from 90% to 96%. Higher electric fields inhibited grain growth due to the lowering of the flash temperature and an accelerated sintering rate. During flash sintering, alumina reacted with the spinel phase to form a high‐alumina spinel solid solution, identified by electron dispersive spectroscopy and from a decrease in the spinel lattice parameter as measured by X‐ray diffraction. It is proposed that the solid solution reaction was promoted by a combination of electrical field and Joule heating.     

Fabrication of Si3N4 preforms from Si3N4 produced via CRN technique

Ceramic preforms with randomly distributed particles as reticulated porous structure which are generally used for metal infiltration as reinforcement, membranes, catalyst supports etc. Preforms are characterized by open porosity making possible their infiltration by liquid metal alloys. In this work, quartz powders using carbon black as a reducing agent were used for alpha Si₃N₄ powders synthesis through a carbothermal reduction and nitridation (CRN) process. The CRN process was carried out under nitrogen flow at 1,450 °C for 4 h. At high temperatures, carbon as reducing agent reacts with the oxygen of SiO₂, and the resulting metallic silicon compounds with nitrogen gas to obtain silicon nitride powder. The reacted powders were used to obtain reticulated ceramic by replica method. The powders containing various bentonite ratios were mixed in water to prepare slurry. The slurry was infiltrated into a polyurethane sponge. A high porous ceramic foam (preform) structure was achieved after burn out of the sponge. All ceramic preforms were sintered to increase stiffness (in the temperature range 900–1,350 °C). The sintered ceramic foams were subjected to compressive tests. The scanning electron microscopy was used to examine the reticulated ceramic foam structure, and X-ray diffraction analysis was performed to determine phases.     

Novel simple solvent-less preparation,characterization and degradation of the cationic dye over holmium oxide ceramic nanostructures

Pure holmium oxide ceramic nanostructures were prepared via a new simple approach. Nanostructures were synthesized by heat treatment in air at 600 °C for 5 h, utilizing [Ho L(NO₃)₂]NO₃ (L=bis-(2-hydroxy-1-naphthaldehyde)-butanediamine Schiff base ligand), as precursor, which was prepared via a solvent-free solid–solid reaction from different molar ratios of holmium nitrate and Schiff base ligand. The as-prepared nanostructures were characterized by field emission scanning electron microscopy (FESEM), thermo-gravimetric analysis (TGA), X-ray diffraction (XRD), energy dispersive X-ray microanalysis (EDX), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. It was found that the calcination temperature and molar ratio of holmium nitrate and Schiff base ligand have significant and key effect on the morphology and particle size of the holmium oxide. To investigate the catalytic properties of as-obtained holmium oxide nanostructures, the photocatalytic degradation of rhodamine B as cationic dye under ultraviolet light irradiation was performed.