Hydrothermal preparation of fractal dendrites: Cerium carbonate hydroxide and cerium oxide

The surfactant-assisted hydrothermal route was used to prepare fractal dendrite cerium carbonate hydroxide (CeOHCO₃) microstructures. After annealing at 600 °C for 4 h, the products were transformed to CeO₂. The crystal structures of the two compounds were determined by X-ray diffraction (XRD). The morphologies and microstructures were characterized by field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM). Room temperature photoluminescence (PL) showed that a strong ultraviolet emission at 336 nm was observed for CeOHCO₃, and that centered at 415 nm for CeO₂ microstructures. Both of these emission peaks are different from those reported for CeOHCO₃ and CeO₂ with other shapes. In addition, the possible growth mechanism of dendrite CeOHCO₃ microstructures and the role of surfactant polyvinyl pyrrolidone (PVP) were also investigated in this paper.     

β-Cyclodextrin-assisted preparation of hierarchical walnut-like CeOHCO3 and CeO2 mesocrystals

The hierarchical walnut-like CeOHCO₃ mesocrystals were prepared by a facile hydrothermal method under low temperature with β-cyclodextrin (β-CD) as assistant agent. The hierarchical walnut-like CeO₂ mesocrystals were obtained by thermal decomposition of CeOHCO₃ mesocrystals. The crystal phase, morphology, and structure of CeOHCO₃ and CeO₂ mesocrystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The time-dependent experimental results indicated that the morphology transformation from shuttle-like to walnut-like and the crystal phase transformation from orthorhombic to hexagonal simultaneously occurred in the formation processes of CeOHCO₃ mesocrystals. On the basis of the morphological and crystal phase evolution processes, the formation mechanism of hierarchical walnut-like CeOHCO₃ mesocrystals, including dissolution-recrystallization processes, was discussed. β-CD was believed to play an important role in the formation of the hierarchical walnut-like CeOHCO₃ mesocrystals. The effects of reaction temperature, β-CD amount, and concentration of reactants on the morphologies of the products were systematically studied. CeO₂ mesocrystals exhibited the distinct red-shift phenomenon in UV-vis absorption spectra.     

Solution combustion synthesis of CeO2-CeAlO3 nano-composites by mixture-of-fuels approach

Nano-composites of CeO₂-CeAlO₃ are synthesised by solution combustion method employing (a) urea and (b) a mixture of urea and glycine as fuels with corresponding metal nitrates. The as-prepared powders are all nano-sized (5-30 nm) and the same is confirmed by broadening of the X-ray diffraction peaks and transmission electron microscopy. A starting composition of Ce:Al in the atomic ratio 4:6 gives rise to different phases depending on the fuel being used for combustion. When urea alone is used as fuel, nano-crystalline CeO₂ phase is formed with Al₂O₃ being in the amorphous state. When the mixture of fuels is used, a mixture of nano-sized CeO₂ and CeAlO₃ phases is obtained. However, upon sintering at 1400 ° C in air, the stable phases CeO₂ and -Al₂O₃ are formed in both the cases. Combustion synthesis using mixture-of-fuels is proposed to be a route to stabilise low oxidation compounds such as CeAlO₃.     

Low-temperature sintering characteristics of nano-sized BaNd2Ti5O14 and Bi2O3–B2O3–ZnO–SiO2 glass powders prepared by gas-phase reactions

Nano-sized BaNd₂Ti₅O₁₄ (BNT) powders were prepared by spray pyrolysis from solutions containing ethylenediaminetetraacetic acid and citric acid. Treatment at temperatures ≥900 °C and subsequent milling resulted in nanoparticle powders with orthorhombic crystal structures. The mean particle size of the powder post-treated at 1000 °C was 160 nm. Nano-sized Bi₂O₃–B₂O₃–ZnO–SiO₂ glass powder with 33 nm average particle size was prepared by flame spray pyrolysis and used as a sintering agent for the BNT. BNT pellets sintered at 1100 °C without the glass had porous structures and fine grain sizes. Those similarly sintered with the glass had denser structures and larger grains.     

Control of particle size and shape of precursors for ceria using ammonium carbonate as a precipitant

Spherical nanocrystalline precursors of ceria (CeO₂) and CeO₂ powder with different size distributions were prepared by a reflux method using cerium nitrate hexahydrate (CN) as the cerium source and ammonium carbonate (AC) as the precipitant. The crystalline phases of the synthesized CeO₂ precursors were identified as orthorhombic Ce₂O(CO₃)₂·H₂O and hexagonal CeCO₃OH. The particle size and shape could be easily controlled by the CN concentration and the ratio of [AC]/[CN]. The CeO₂ precursors were calcined at 400-700 °C to obtain CeO₂. The particle size distribution and morphology of the synthesized CeO₂ powders were unaffected by the calcination. The specific surface area of the CeO₂ powders was increased by the release of CO₂ and H₂O during the calcination. The calcination temperature is an important factor for the preparation of CeO₂ powder with a high surface area.     

Preparation and characterization of nanometer-scale powders ceria by electrochemical deposition method

Ceria (CeO₂) nanoparticles of 10-30 nm in average particle size have been synthesized via electrochemical deposition method in cerium(III) chloride solution with an undivided cell as electrochemical cell and ethanol-acetylacetone as additives. X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transformation infrared spectroscopy (FT-IR) and thermal analysis (TG-DTA) are introduced to characterize the samples. The results indicate that the as-prepared powders after being treated at 650 °C are nanocrystalline with the cubic fluorite structure and the sphericity in shape. It is revealed that the size of ceria nanoparticles can be decreased effectively by adding the ethanol-acetylacetone solution. In addition, the possible formed mechanism of CeO₂ nanometer-scale powder. The role of additive is also investigated in this paper.     

Dopant induced variations in microstructure and optical properties of CeO2 nanoparticles

Nanocrystalline CeO₂ particles doped in the range of 0-20% of Ca²⁺, La³⁺, and Zr⁴⁺ have been prepared from hydrothermal synthesis of nitrate solutions at 200 °C and the influences of the dopants on microstructure and optical properties of the nanoparticles have been investigated. The unit cell parameter is found to be modified by −0.39, +0.83 and +0.16% for doping of 20% Zr⁴⁺, La³⁺, and Ca²⁺, respectively. For each batch prepared, nanoparticles with a narrow size distribution of 5-15 nm have been obtained. A high-resolution transmission electron microscopy investigation reveals that these particles are single crystals mostly having hexagonal, square or circular two-dimensional projections. UV-visible spectra of doped powders exhibit shift of the absorption edge and absorption peak with respect to those of the undoped CeO₂ particles and has been attributed to compensation of Ce³⁺ and decreasing crystallite size as result of doping.     

On the green density, sintering behavior and electrical property of tape cast Ce0.9Gd0.1O1.95 electrolyte films

Gadolinia doped ceria (Ce_0.9Gd_0.1O_1.95, GDC) electrolyte films were tape cast from oxalate coprecipitated GDC powders, gelcast GDC powders and their mixtures, respectively, to evaluate the effects of the original particle size and distribution on the properties of the green and sintered GDC cast tapes. The apparent density of different original powders, as well as the green density, sintered behavior, and electrical conductivity of tapes cast from the various starting powders were investigated. Mixing the coprecipitated and the gelcast GDC powders not only results in a higher packing efficiency of particles in the loose powders, but also results in higher green and sintered densities of cast tapes. Furthermore, tapes cast from the 50/50 powder mixtures can be sintered to 96.2% of theoretical density at relatively low sintering temperature of 1400°C, whereas those from the oxalate coprecipitated and from the gelcast powders were only 89.7 and 94.1% dense, respectively. The ac impedance measurement shows that GDC films cast from the 50/50 powder mixture exhibit good electrical conductivity (4.2 and 6.0 S m⁻¹ at 700 and 800°C in air, respectively). The test results have revealed that high-density GDC films can be fabricated by tape casting technique at relatively low sintering temperature by optimizing the particle size distribution of the starting powders.     

Control of the particle size and morphology of hydrothermally synthesised lead zirconate titanate powders

The particle size and morphology of hydrothermally synthesised lead zirconate titanate (PZT) powders can be controlled by concentrations of the mineraliser such as potassium hydroxide (KOH), and the hydrothermal synthesis temperature and time, which all influence the particle nucleation and growth mechanisms. The mineraliser is crucial in facilitating both the in-situ transformation process during the nucleation stage and the nuclei-coagulation process during the subsequent growth stage. Its concentration must be high enough to ensure the formation of only pure perovskite PZT particles but low enough to prevent excessive PZT particle growth. The minimum necessary mineraliser concentration has, however, strong dependence on both the hydrothermal synthesis temperature and chemical environment in hydrothermal solution. Thus, perovskite PZT powders with ca. 200 nm particle size and narrow particle size distribution can be synthesised hydrothermally at 300°C using KOH as a mineraliser with a minimum concentration of 0.4 M.     

Hydrothermal precipitation and characterization of nanocrystalline BaTiO3 particles

Crystalline BaTiO₃ powders were precipitated by reacting fine TiO₂ particles with a strongly alkaline solution of Ba(OH)₂ under hydrothermal conditions at 80°C to 240°C. The characteristics of the powders were investigated by X-ray diffraction, transmission electron microscopy, thermal analysis and atomic emission spectroscopy. For a fixed reaction time of 24 hours, the average particle size of BaTiO₃ increased from 50 nm at 90°C to 100 nm at 240°C. At synthesis temperatures below 150°C, the BaTiO₃ particles had a narrow size distribution and were predominantly cubic in structure. Higher synthesis temperatures produced a mixture of the cubic and tetragonal phases in which the concentration of the tetragonal phase increased with increasing temperature. A bimodal distribution of sizes developed for long reaction times (96 h) at the highest synthesis temperature (240°C). Thermal analysis revealed little weight loss on heating the powders to temperatures up to 700°C. The influence of particle size and processing-related hydroxyl defects on the crystal structure of the BaTiO₃ powder is discussed.     

Novel synthesis of TiN fine powders by nitridation with ammonium chloride

TiN fine powders were prepared by the reaction of TiH₂ with ammonium chloride at various temperatures under a flow of N₂/H₂ mixed gas. In a temperature range of 500-800°C, the powder samples obtained had a particle size of 3-20 nm, and a specific surface area of 30-60 m²/g. The particle size increased with the increase of the reaction temperature. The lattice parameters and the chemical analysis data showed that the TiN powder had the stoichiometric composition. The TiN powder prepared at temperatures of 600-800°C showed superconductivity with a transition temperature of 4.0-4.5 K.     

Synthesis of BaZrO3 by a solid-state reaction technique using nitrate precursors

High phase purity barium metazirconate powders have been synthesized from a modified solid-state reaction. Reactive powders consisting of submicron particles and narrow particle size distribution were obtained by heating a 1:1 molar mixture of barium nitrate and zirconyl nitrate at 800°C up to 8 h. Simultaneous thermal analysis (TG-DTA) assisted in elucidating the probable reaction pathways leading to the formation of the target compound in the BaO-ZrO₂ system. Systematic structural and microstructural characterization on the green powders and the compacts sintered up to 1700°C were carried out. A two-stage sintering schedule consisting of a 6 h soak at 1600°C followed by slow heating up to 1700°C with no dwell, led to highly dense microstructural features.     

The synthesis and optical property of solid-state-prepared YAG:Ce phosphor by a spray-drying method

Ce³⁺-activated yttrium aluminum garnet (Y₃Al₅O₁₂:Ce, YAG:Ce) powder as luminescent phosphor was synthesized by the solid-state reaction method. The phase identification, microstructure and photoluminescent properties of the products were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), absorption spectrum and photoluminescence (PL) analysis. Spherical phosphor particle is considered better than irregular-shaped particle to improve PL property and application, so this phosphor was granulated into a sphere-like shape by a spray-drying device. After calcinating at 1500 °C for 0, 4, and 8 h, the product was identified as YAG and CeO₂ phases. The CeO₂ phase content is decreased by increasing the calcination time or decreasing the Ce³⁺ doping content. The product showed higher emission intensity resulted from more Ce³⁺ content and larger grain size. The product with CeO₂ was found to have lower emission intensity. This paper presents the crystal structures of Rietveld refinement results of powder XRD data.     

Powder synthesis and characterization of nanocrystalline CeO2 via the combustion processes

Nanocrystalline CeO₂ powders were synthesized by the combustion reactions using citric acid and glycol as fuels and nitrate as an oxidant. The adiabatic flame temperatures in the auto ignition processes of the precursors were calculated theoretically. XRD measurements indicated that the powders produced in the combustion processes were cubic fluorite CeO₂ phase. The size and morphology of the particles and extent of agglomeration in the powders were studied using transmission electron microscopy (TEM) and the particle size analyzer respectively. Blue shifts of the absorption peak of the as-prepared powders were observed.     

Formation and control of mechanism for the preparation of ultra-fine barium strontium titanate powders by the citrate precursor method

A modified citrate precursor method, combining the advantages of the nitrate autocombustion method by introducing the nitric acid, was successfully used to synthesize ultrafine Ba_0.70Sr_0.30TiO₃ powders. Slight agglomerated and homogenized BST powders, with an average particle size of 20 nm, were obtained at 800 °C. Combining the results of TG/DTA and XRD, it can be concluded that the formation of BST powders takes place via two reaction mechanisms: decomposition of an intermediate oxycarbonate mechanism (DIOm) at low temperature, and solid-state reaction mechanism (SSRm) between nanocrystalline carbonates and amorphous TiO₂ at high temperature. TEM shows higher amount of CA led to BST powders of better quality in morphology. Based on results of chemical analysis, it is suggested that higher amount of CA drives the mechanism to tend to DIOm. By simply adjusting the ratio of reagents, the reaction mechanism can be dominated and we can greatly control the final morphology of the powders.     

Crystallization behavior of nano-ceria powders by hydrothermal synthesis using a mixture of H2O2 and NH4OH

Homogeneous and well-crystallized nano-ceria (CeO₂) powders were produced by hydrothermal synthesis using a mixture of H₂O₂ as the oxidizer and NH₄OH as the mineralizer. The precipitates were prepared by mixture ligands of OH and OOH derived from NH₄OH and H₂O₂. The hydrothermal synthesis was conducted at 200 °C for 6 h.The synthesized ceria powders were characterized as the crystalline phase identification by X-ray diffractometry, the chemical bonding by infrared spectrophotometer (FT-IR) and the morphology and particle size by transmission electron microscopy (TEM).Crystallization behavior of ceria powders using a mixture of oxidizer and mineralizer was more influenced by OOH ligands than by OH ligands to form Ce(OH)_x(OOH)_4−x as precursor with increasing concentrations of H₂O₂ with 10–20 times of the cerium(III) ion. In all samples, synthesized particle size was decreased with increasing concentration of oxidizer ranging from 6 to 12 nm in diameter. Morphology and size distribution of synthesized particles were relatively spherical and uniform, respectively.     

Hydrothermal synthesis of CeO2 nano-octahedrons

CeO₂ nano-octahedrons were synthesized with a facile hydrothermal synthesis process where Ce(NO₃)₃·6H₂O and urea were used as a cerium resource and mineralizer respectively and no surfactant or template was applied. The effects of synthesis parameters such as reaction temperature, reaction time, as well as the dosages of Ce (NO₃)₃·6H₂O and urea were studied. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis were conducted to characterize the crystalline and morphology of the obtained CeO₂ powders. The optimal reaction condition to prepare the CeO₂ of the desired fluorite structure was established. The possible mechanism of synthesis of CeO₂ with a nano-octahedron morphology was illustrated.     

Luminescent properties of YAG:Ce phosphor powders prepared by hydrothermal-homogeneous precipitation method

Y_3 − xCe_xAl₅O₁₂ (YAG:Ce³⁺) phosphor powders were successfully prepared by hydrothermal-homogenous precipitation (HHP) method, under mild conditions with inexpensive aluminum and yttrium nitrates as the starting materials and urea as homogenous precipitant. The pure YAG crystalline phase could be formed after hydrothermal treatment at 100 °C for 4 h and 240 °C for 20 h and postannealing process at 1200 °C for 2 h. All of the as-prepared YAG:Ce³⁺ powders did not have the CeO₂ phase. The photoluminescence spectrum of crystalline YAG:Ce³⁺ phosphors showed the emission intensity of phosphor increased with increasing the annealed temperature and reached its maximum as the molar fraction of cerium ion was 0.10, and also showed the maximum emission wavelength nearly unchanged with the calcination temperature and cerium doping concentration.     

Novel wet-chemical synthesis and characterization of nanocrystalline CeO2 and Ce0.8Gd0.2O1.9 as solid electrolyte for intermediate temperature solid oxide fuel cell (IT-SOFC) applications

Novel wet-chemical methods of synthesis have been adopted to synthesize nano-crystalline CeO₂ and Gd-substituted compositions aiming to explore an efficient oxide ion conducting solid electrolyte for intermediate temperature solid oxide fuel cell (IT-SOFC) applications. Nano-crystalline CeO₂ powders were synthesized by combustion method using redox mixture of cerric ammonium nitrate or cerium nitrate and maleic acid or 1,3-dimethylurea and compared with high surface area CeO₂ powders prepared by hydrothermal technique with microwave precipitated precursor from aqueous solutions of (NH₄)₂Ce(NO₃)₆ and urea. The grain size achieved by the hydrothermal technique is ∼7 nm which is smaller than that of commercial nano CeO₂ powders. Conventional or microwave sintering was used to prepare dense Ce_0.8Gd_0.2O_1.9 pellets from the ceria powders made of redox mixture of cerium nitrate, 1,3-dimethylurea (DMU) and Gd₂O₃ as the starting ingredients. The samples were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and ac impedance spectroscopy. The ionic conductivity measured for the pellet sintered at 1400 °C is 1 × 10⁻² and 2.4 × 10⁻² S/cm at 700 °C and 800 °C respectively.     

Synthesis of single-crystalline Ce(CO3)(OH) with novel dendrite morphology and their thermal conversion to CeO2

Single-crystalline cerium carbonate hydroxide (Ce(CO₃)(OH)) with dendrite morphologies have been successfully synthesized by hydrothermal method at 150 °C using Ce(NO₃)₃·6H₂O as the cerium source, aqueous carbamide as both an alkaline and carbon source and poly(vinyl pyrrolidone) (PVP) as surfactant. Ceria (CeO₂) with dendrite morphologies have been fabricated by a thermal decomposition-oxidation process at 500 °C for 6 h using single-crystalline Ce(CO₃)(OH) dendrites as the precursor. The dendrite morphologies of Ce(CO₃)(OH) was sustained after thermal decomposition-oxidation to CeO₂. The as-prepared products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), and thermogravimetric analysis (TG).