Reactive Cerium(IV) Oxide Powders by the Homogeneous Precipitation Method

CeO₂ powders have been prepared by aging a cerium(III) nitrate solution in the presence of hexamethylenetetramine. Oxidation of Ce³⁺ occurs in the precipitate and the wet precipitate is identified as crystallized CeO₂ before any heat treatment. The cold-pressed powders can be sintered to full density at temperatures as low as 1250°C in just 6 min. Moreover, the sinterability of the powders is insensitive to the calcination temperatures, particle size, or green density. The powders calcined at 850°C with a crystallite size of 600 Å have a sinterability as good as the powders calcined at 450°C with a crystallite size of 145 Å. The mechanisms for direct CeO₂ precipitation and its relation to the excellent sinterability are discussed.     

Electrochemical Synthesis and Sintering of Nanocrystalline Cerium(IV) Oxide Powders

Nanocrystalline CeO₂ powders were prepared electrochemically by the cathodic electrogeneration of base, and their sintering behavior was investigated. X-ray diffraction and transmission electron microscopy revealed that the as-prepared powders were crystalline cerium(IV) oxide with the cubic fluorite structure. The lattice parameter of the electrogenerated material was 0.5419 nm. The powders consisted of nonaggregated, faceted particles. The average crystallite size was a function of the solution temperature. It increased from 10 nm at 29°C to 14 nm at 80°C. Consolidated powders were sintered in air at both a constant heating rate of 10°C/min and under isothermal conditions. The temperature at which sintering started (750°C) for nanocrystalline CeO₂ powders was only about 100°C lower than that of coarser-grained powders (850°C). However, the sintering rate was enhanced. The temperature at which shrinkage stopped was 200°-300°C lower with the nanoscale powder than with micrometer-sized powders. A sintered specimen with 99.8% of theoretical density and a grain size of about 350 nm was obtained by sintering at 1300°C for 2 h.     

Hydrothermal Synthesis of Nanocrystalline Cerium(IV) Oxide Powders

Nanocrystalline cerium(IV) oxide (CeO₂) powders were prepared by heating solutions of cerium(IV) salts in the presence of urea under hydrothermal conditions at 120° to 180°C. The effects of the concentration of urea and hydrothermal treatment temperature on the morphology and crystallite size of the synthesized particles were investigated. The synthesized particles were angular, ultrafine CeO₂, with a cubic fluorite structure. Their crystallite size decreased from 20 to 10 nm with increasing urea concentration from 2 times to 8 times that of the Ce⁴⁺ ion. The size only slightly changed by calcining at temperatures below 600°C.     

Synthesis and Characterization of Nanoscaled Cerium (IV) Oxide via a Solid-State Mechanochemical Method

Solid-state reactions have the potential for direct preparation of ceramic powders and offer a low-temperature and low-cost alternative to conventional techniques for production of oxide powders. This paper describes a simple and effective mechanochemical method based on solid-state reactions during ball milling for synthesis of nanoscaled ceria (CeO₂) particles. By using an organic base instead of an inorganic base, metal-ion-free nanoscaled CeO₂ can also be made. The effects of annealing temperature on particle sizes and lattice strain are investigated. The results show that the average particle sizes of the particles increases and the average crystal lattice distortion decreases with the annealing temperature. Transmission electron microscopy examinations demonstrate that the CeO₂ particles synthesised by this method are near-spherical shaped.     

Characterization of Thermoelectric Metal Oxide Elements Prepared by the Pulse Electric-Current Sintering Method

Thermoelectric elements consisting of the layered polycrystalline materials of Al-doped ZnO and NaCo₂O₄ were prepared using the pulse electric-current sintering (PECS) method at 900°C for 3 min. Direct contact between the polycrystalline Al-doped ZnO and the NaCo₂O₄ was obtained in a single-step process for the stacked powders. The electrical conductivities of the polycrystalline materials prepared by PECS were higher than those of materials prepared by conventional sintering, despite their porous structure. The thermoelectric voltage of the 1-mol%-Al-doped ZnO and NaCo₂O₄ polycrystalline element (measuring ∼6 mm × 3 mm × 15 mm) was 83 mV at d T = 500 K, when the junction of the elements was at 800°C.     

Synthesis and Sintering of Cerium(III) Sulfide Powders

Cerium(III) sulfide (Ce₂S₃) powder was synthesized via the sulfurization of ceria (CeO₂) powder using carbon disulfide gas. Single-phase α-Ce₂S₃ could be formed via sulfurization at 973 K for 28.8 ks. The preparation of α-Ce₂S₃ became feasible at low temperature, in comparison to sulfurization using hydrogen sulfide gas. According to the fact that the formation of α-Ce₂S₃ was accelerated by the addition of carbon black to the CeO₂ powder, carbothermic reduction was considered to become a dominant reaction, as the temperature increased. To obtain the activation energy for the densification of β-Ce₂S₃ powder, which was prepared by vacuum heating α-Ce₂S₃, the data of densification by hot pressing was analyzed by a kinetic equation that was proposed by other researchers. As a result, the sintering behavior could be best explained by a grain-boundary-diffusion mechanism that had an apparent activation energy of 382 kJ/mol.     

Hydrothermal Synthesis of Cerium(IV) Oxide

CeO₂ powders have been prepared from cerium(III) nitrate, cerium(IV) sulfate, and cerium(IV) ammonium sulfate under hydrothermal conditions at 120° to 200°C for 5 to 40 h. The effects of the starting cerium compounds, hydrothermal treatment temperature, and the concentration of the solutions on the crystal growth of CeO₂ were investigated. CeO₂ powders hydrothermally synthesized at 180°C for 5 h from cerium(IV) salts had very fine particle sizes (30 Å); on the other hand, the powder from the cerium(III) salt had a relatively coarse particle size (160 Å). Although the crystallite size of the powder synthesized from the cerium(IV) compounds depended on the treatment temperature, that from the cerium(III) compound was insensitive to the treatment temperature. The mechanisms for the growth of CeO₂ particles under hydrothermal conditions are discussed.     

Effect of pH of Medium on Hydrothermal Synthesis of Nanocrystalline Cerium(IV) Oxide Powders

Well-crystallized cerium(IV) oxide (CeO₂) powders with nanosizes without agglomeration have been synthesized by a hydrothermal method in an acidic medium by using cerium hydroxide gel as a precursor. The relationship between the grain size, the morphology of the CeO₂ crystallites, and the reaction conditions such as temperature, time, and acidity of the medium was studied. The experiments showed that with increasing reaction temperature and time, the CeO₂ crystallites grew larger. The crystallites synthesized in an acidic hydrothermal medium were larger and had a more regular morphology than the ones synthesized in a neutral or alkaline medium when the reaction temperature and time were fixed. The CeO₂ crystallites synthesized in an acidic medium were monodispersed; however, there was vigorous agglomeration among the grains synthesized in a neutral or alkaline medium. It was demonstrated that the hydrothermal treatment was an Ostwald ripening process and the acidity (pH) of the used hydrothermal medium played a key role in the dissolution of smaller grains. It is proposed that the dissolution process can control the kinetics of the growth of larger grains.     

气凝合成纳米氧化锰粉体的特性研究

以气相凝结法制作纳米氧化锰粉体,利用制程参数控制粒径大小、形状与相组成,并以透射电子显微镜、X光衍射分析、示差扫瞄热量测定仪与同步辐射临场(in situ)X光衍射分析技术进行相关特性检测,了解使用氧化锰的超级电容器材料的基本性质.     

Effect of Cobalt(II) Oxide and Manganese(IV) Oxide on Sintering of Tin(IV) Oxide

Additions of 0. 5 to 2. 0 mol% of CoO or MnO₂ onto SnO₂ promote densification of this oxide up to 99% of theoretical density. The temperature of the maximum shrinkage rate ( T_M ) and the relative density in the maximum densification rate (p*) during constant sintering heating rate depend on the dopant concentration. Thus, dopant concentration controls the densifying and nondensifying mechanisms during sintering. The densification of SnO₂ witih addition of CoO or MnO₂ is explained in terms of the creation of oxygen vacancies.     

Synthesis of Cerium(IV) Oxide Ultrafine Particles by Solid-State Reactions

CeO₂ ultrafine particles were prepared by solid-state reactions at room temperature. These particles were found to have very fine particle sizes (∼3 nm) with a fluorite structure ( a = 5.42 Å). BET measurements showed that the surface area of the particles was 96.2 m²/g. The use of two different precursors was found to affect the size of the CeO₂ particles. We discuss the effect of calcination at different temperatures on the morphology, size, and BET surface area of CeO₂ particles. A salt byproduct coating prevented agglomeration of the CeO₂ particles.     

Formation and Sintering of Yttria-Doped Tetragonal Zirconia with 50 mol% Alumina Prepared by the Hydrazine Method

Al₂O₃/Y₂O₃-doped ZrO₂ composite powders with 50 mol% Al₂O₃ are prepared by the hydrazine method. As-prepared powders are mixtures of AlO(OH) gel and amorphous ZrO₂ solid solutions containing Y₂O₃ and Al₂O₃. The formation process leading to α-Al₂O₃- t -ZrO₂ composite powders is examined. Hot isostatic pressing is performed for 2 h at 1400°C under 196 MPa using θ-Al₂O₃- t -ZrO₂ composite powders. The resulting dense, sintered α-Al₂O₃- t -ZrO₂ composites show excellent mechanical strength.     

Formation of Alumina/Zirconia (3 mol% Yttria) Composite Powders Prepared by the Hydrazine Methods

Alumina/3 mol% yttria-doped zirconia composite powders have been prepared by the hydrazine method. As-prepared powders are AlO(OH) gel solid solutions and the mixtures of this and amorphous ZrO₂ below and above 10 mol% ZrO₂, respectively. The formation process leading to α–Al₂O₃– t -ZrO₂ composite powders is examined.     

Formation, Powder Characterization and Sintering of MgCr2O4 by the Hydrazine Method

Picrochromite (MgCr₂O₄) crystallizes at 480° to 530°C from an amorphous material prepared by the hydrazine method. The MgCr₂O₄ powders were characterized for particle size and surface area. Individual particles tend toward a hexagonal morphology above 1000°C. Dense MgCr₂O₄ ceramics (99.5% of theoretical) with an average grain size of 2 μm have been fabricated by spark plasma sintering for 5 min at 1400°C and 30 MPa. Their fracture toughness and bending strength are 3.7 MPa·m^1/2 and 310 MPa, respectively.     

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.     

Enhanced Properties of Tin(IV) Oxide Based Materials by Field-Activated Sintering

The densification of SnO₂ (0.9 mol)–Sb₂O₃ (0.1 mol) solid solution without any additives was studied by conventional and field-activated sintering technique (FAST). FAST sintering achieved a relative density value of 92.4% at 1163 K for 10 min versus 61.3% in conventional sintering at 1273 K for 3 h. An abnormal reduction of the IR transmittance and a semiconductor defect structure with only one donor level in the SnO₂ energy gap were noticed in the FAST-sintered as compared with the conventionally sintered Sn_0.82Sb_0.18O₂ solid solution. A high charge carrier concentration (i.e., electronic conduction) was shown in the FAST-sintered sample by conductivity measurements and the negative values of the Seebeck coefficient.     

Conventionally Prepared Submicrometer Lead-Based Perovskite Powders by Reactive Calcination

Submicrometer powders of various Pb-based perovskites, including PbTiO₃, PbZrO₃, Pb(Zr_0.53Ti_0.47)O₃, and Pb(Mg_1/3Nb_2/3)O₃ were prepared by a reactive calcination process. Using only reagent-grade raw materials and conventional processing techniques, highly reactive powders were produced by reacting the materials near the temperature of maximum volumetric expansion. At this point, the morphological development results in a skeletal-type structure consisting of ultrafine particulates that can be readily broken down further by milling. Powder sizes less than 0.3 μm and as small as 70 nm generally only achievable using chemical processing techniques were achieved. The highly reactive powders allowed densification to occur at temperatures as low as ∼900°C with correspondingly small grain sizes. A model describing the physiochemical behavior and associated morphological development of Pb-based perovskites was herein proposed.     

ESR Study of Cerium (IV) Oxide in Vacuum Air and Hydrogen

Cerium (IV) oxide prepared at high temperatures in air shows ESR absorption signals. The oxide prepared at low temperatures shows very diffuse signals. Heating the oxide in vacuum at 1000° or in hydrogen at 298° results in a reduction of the intensity of the signal. A theory was developed to show that the ESR signal is obtained from the quasi free electron in non-stoichiometric ceria.     

Sintering of Fine Oxide Powders: II, Sintering Mechanisms

Conventional and new sintering mechanisms have been investigated using fine powders of CeO₂ and Y₂O₃ of excellent sinterability. We have verified the validity of Herrings scaling law for 60%–84% relative density and found that it is consistent with grain-boundary-diffusion control. At lower densities, we have found that pores larger than the critical size, in the sense of Kingery and Francois, can still be sintered readily. This is rationalized by a new sintering mechanism based on particle repacking concurrent with particle coarsening, resulting in a higher packing factor. Very fine, surface-active powders that coarsen rapidly are uniquely capable of taking advantage of this new sintering mechanism, which along with their propensity to homogenization, accounts for their remarkable sinterability even at very low green densities.     

Preparation and Properties of Tricyclopentadienyl Cerium (IV) Chloride and Bisindenyl Cerium (IV) Dichloride

The reactions of dipyridinium cerium (IV) hexachloride with tetracyclopentadienyl cerium or sodium cyclopentadienide and tetraindenyl cerium or sodium indenide in tetrahydrofuran yield tricyclopentadienyl cerium (IV) chloride and bisindenyl cerium (IV) dichloride. Infrared spectra, thermal stabilities and other characteristics of the compounds have been studied.