Synthesis of Nanocrystalline Zirconium Nitride Powders by Reduction–Nitridation of Zirconium Oxide

Nanocrystalline ZrN powder was synthesized by reduction–nitridation of nanosized ZrO₂ powder in ammonia gas with magnesium as the reducing agent. The effects of nitridation temperature, holding time, and Mg:ZrO₂ mole ratio on the powder properties were investigated. Cubic phase ZrN powder with a 30–100-nm particle size was synthesized at 1000°C for 6 h, under a Mg:ZrO₂ mole ratio of 10:1.     

Synthesis of Niobium(V)-Stabilized Tetragonal Zirconia Nanocrystalline Powders

The polymer precursor method is very useful to prepare Nb⁵⁺-stabilized nanocrystalline powders of t -ZrO₂. The precursor solution is composed of zirconium oxalate, niobium tartrate, and poly(vinyl alcohol), which help to form a network matrix to disperse the metal ions homogeneously. Nb⁵⁺ is an effective agent to stabilize t -ZrO₂, and ease of formation of the tetragonal phase increases with increasing dopant concentration. Thermal stability of t -phase is found up to 1700°C having 15 mol% Nb⁵⁺, prepared at 600°C with particle sizes of 35 ± 5 nm.     

Hydrothermal Synthesis of Weakly Agglomerated Nanocrystalline Scandia-Stabilized Zirconia

A pure cubic phase of weakly agglomerated, nanocrystalline, 8-mol%-Sc₂O₃-stabilized zirconia (8ScSZ) was synthesized by a two-step hydrothermal treatment in the presence of urea: a stock solution of metal nitrates and urea was heated at 80°C for 48 h and then at 180°C for 72 h. The omission of the first low-temperature treatment resulted in more monoclinic phase. The effects of urea concentration and calcining temperature on the crystallization of the as-synthesized nanocrystalline 8ScSZ are also discussed.     

Microwave-Hydrothermal Synthesis and Hyperfine Characterization of Praseodymium-Doped Nanometric Zirconia Powders

This work focuses on the microwave-assisted hydrothermal synthesis of praseodymium-doped zirconia and on the subsequent evaluation of the effect of synthesis conditions on powder properties. Pure and 10 mol% Pr-doped zirconia samples have been analyzed by X-ray diffraction (XRD) and the perturbed angular correlations hyperfine technique, which probes the nearest environments of zirconium ions. At atomic scale, as determined from perturbed angular correlation data, the XRD amorphous fraction of the as-obtained powders exhibits a tetragonal-like structure. The pure powder becomes partially stabilized and the doped powder is a substitutional solid solution of praseodymium in tetragonal zirconia.     

Synthesis and Characterization of Nanocrystalline Niobium Nitride Powders

Nanocrystalline NbN powder was synthesized by the direct nitridation of amorphous Nb₂O₅ powder with high BET surface area. X-ray diffractometry analysis indicated that the cubic-phase NbN powder could be obtained by nitridation at 650°–800°C for 3–8 h. Transmission electron microscopy images showed that the particle sizes were in the range of 15–40 nm. The effect of the nitridation temperature and holding time on the powder properties was discussed.     

Effect of Nb2O5/ZnO Addition on Microwave Properties of (Zr0.8Sn0.2)TiO4 Ceramics

The effects of Nb₂O₅ and ZnO addition on the dielectric properties, especially the quality factor, of (Zr_0.8Sn_0.2)TiO₄ (ZST) ceramics were investigated in terms of the sintered density acquired by the zinc. For ZST ceramics with 2 mol% added ZnO, the relative density of the samples decreased with >0.5 mol% addition of Nb₂O₅. On the other hand, for samples with 6 mol% added ZnO, the relative density remained >97%, even when the amount of Nb₂O₅ was increased to 2.0 mol%. When >0.5 mol% Nb₂O₅ was added, both the quality factor and the dielectric constant exhibited similar trends with sintered density. The ZST ceramics with 6 mol% added ZnO, especially, still manifested a quality factor >40 000 and a dielectric constant of 37, even when the amount of Nb₂O₅ was increased, values that are not explainable by the previously suggested electronic defect model.     

Synthesis of Nanocrystalline Titanium Nitride Powders by Direct Nitridation of Titanium Oxide

Nanocrystalline TiN powder has been synthesized by the direct nitridation of nanocrystalline TiO₂ powder. Powder XRD patterns indicated that the TiN nanocrystalline powder could be obtained by nitridation at 800°C for 5 h. TEM micrographs showed that the synthesized TiN powders consisted of uniform spherical particles with an average diameter of ∼20 nm. The effect of the nitridation temperature and holding time on the powder properties is 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.     

Nonisothermal Synthesis of Yttria-Stabilized Zirconia Nanopowder through Oxalate Processing: I, Characteristics of Y-Zr Oxalate Synthesis and Its Decomposition

To obtain powder with a composition of 3 mol% Y₂O₃–97 mol% ZrO₂, a process of Y-Zr oxalate powder production has been optimized, to produce an oxalate with minimal particle size. The methodology of the nonisothermal decomposition of Y-Zr oxalate has been explained. Characteristics of the nonisothermal decomposition of different oxalates have been studied. Nanocrystalline Y₂O₃-stabilized ZrO₂ (YSZ) powder with a narrow size distribution of primary particles and aggregates was produced. The zirconia powder that was obtained from the smallest oxalate powder via nonisothermal decomposition had a particle size of 8–10 nm. The YSZ powder was weakly aggregated, with a narrow aggregate-size distribution of 70–90 nm.     

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.     

流沙状氟硅酸钠晶体的制备

研究了利用反应结晶法制备流沙状氟硅酸钠时工艺条件（进料酸浓度、进料方式和结晶器型式）对结晶过程的影响。结果表明：进料H2SiF6的适宜浓度为12％,且保持H2SiF6在晶体生长区过量对晶体长大有利;采用连续结晶器可制得流沙状晶体,晶体粒度分布较好。     

Differences between Zirconium Hydroxide (Zr(OH)4·nH2O) and Hydrous Zirconia (ZrO2·nH2O)

Based on cause and effect rather than experiment data, zirconium hydroxide (Zr(OH)₄· n H₂O) is always considered as hydrous zirconia (ZrO₂· n H₂O). With the aid of nitric acid, XPS, XRD, XPF, and TGA, some differences between them have been confirmed. It is found that in contrast to zirconium hydroxide (the binding energy of zirconium = 183.6 eV), hydrous zirconia does not dissolve in nitric acid. The chemical properties of zirconium (181.8 eV) in hydrous zirconia are similar to those in zirconia (182.2 eV for the binding energy of zirconium), and the weight loss of hydrous zirconia is 21.5%, different from 32.19%, the weight loss of zirconium hydroxide. According to the experimental data, a structure for hydrous zirconia is proposed and then the different phenomena are explained.     

Effect of Phase Transformation on the Densification of Coprecipitated Nanocrystalline Indium Tin Oxide Powders

Two kinds of nanocrystalline indium tin oxide (ITO) powders with different crystal structures—rhombohedral and cubic—were prepared using a coprecipitation process through the control of aging time of precipitates after coprecipitation. The densification characteristics of the two ITO powders were examined. During sintering the rhombohedral ITO, which is a high-pressure phase, was transformed to cubic around 900°C. The phase transformation induced coarsening of grains and many voids in the microstructure retarded densification. On the other hand the cubic ITO, which did not experience phase transformation during sintering, was well densified as the sintering temperature increased. Poor densification of the rhombohedral ITO powder is explained from the viewpoint of coarsening of grains during the phase transformation. This result shows the significance of phase transformation during sintering.     

Low-Temperature Hydrothermal Synthesis of Yttrium-Doped Zirconia Powders

The feasibility of low-temperature synthesis of yttrium-doped zirconia (Y-ZrO₂) crystalline powders in aqueous solutions at lessthan equal to100°C has been evaluated, and the hydrothermal crystallization mechanism for Y-ZrO₂ powders also has been investigated. Coprecipitated (Y,Zr) hydroxide gel, mechanical mixtures of Y(OH)₃ and Zr(OH)₄ gel, and Y(OH)₃ gel have been reacted in boiling alkaline solutions. Coprecipitated (Y,Zr) hydroxide gel crystallized to cubic or tetragonal Y-ZrO₂ at pH 13.9. The yttrium content in the powder synthesized from coprecipitated (Y,Zr) hydroxide is consistent with the initial precursor solution composition, as expected from the similarity in solubility of Zr(OH)^-₅ and Y(OH)^-₄. A diffusionless mechanism for the transformation of the (Y,Zr) hydroxide gel to Y-ZrO₂ is proposed, and the phase stability in aqueous solution is discussed in terms of an in situ crystallization model. It is also demonstrated through thermodynamic arguments with experimental verification that the stable form of the Y-ZrO₂ at 25°C is the anhydrous phase, not the metal hydroxide as previously thought.     

Continuous Processing of Monodispersed Titania Powders

A new continuous precipitation process for monodispersed ceramic powders using a static mixer was developed. Monodispersed TiO₂ powders were prepared continuously with high reproducibility and reliability by controlled hydrolysis of titanium ethoxide. Important steps were uniform and rapid mixing and aging using hydroxypropylcellulose as a dispersant. The concentrations of titanium ethoxide and water suitable to production of monodispersed TiO₂ powders lay within a limited range. A minimum aging period of 10 min was required to obtain monodispersed powders.     

X-ray Diffraction Methodology for the Microstructural Analysis of Nanocrystalline Powders: Application to Cerium Oxide

The microstructural evolution of nanocrystalline ceria produced by sol–gel has been analyzed as a function of the calcination temperature employing a novel nondestructive method based on the modeling of the whole X-ray diffraction pattern. The results have been thoroughly verified by transmission electron microscopy. A variation both in the average size and in the distribution of the crystalline domains is evidenced. In addition, information concerning lattice defects can be inferred on a larger scale than that normally accessible by microscopy techniques.     

纳米颗粒粒径对等离子喷涂法制备氧化锆纳米涂层的影响

利用扫描电镜(SEM)、场发射扫描电镜(FESEM)、透射电镜(TEM)、比表面积吸附法(BET)等分析测试技术,研究了3种不同纳米尺寸氧化锫粉粒的造粒性能、沉积效率以及对等离子喷涂涂层晶粒大小、涂层熔融性能、结合强度的影响.结果表明:纳米氧化锆粉体一次颗粒粒径大小显著影响纳米粉体的喷雾造粒性能、沉积效率、涂层表面粗糙度、涂层晶粒粒径和结合强度大小.本试验中,利用颗粒一次粒径范围为50～70 nm的纳米氧化锆粉体,等离子喷涂制备了晶粒粒径范围为80～120 nm,沉积效率为43%,涂层表面粗糙度为5.92 μm,结合强度为27 MPa的纳米结构氧化锆涂层.     

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.