Chemical reduction of nanocrystalline CeO2

The reduction of commercial and mechanochemically processed CeO₂ powders was studied. Nanostructured CeO₂, with the crystallite size of 21 nm and the lattice distortion of 0.37%, was obtained during 60 min of milling in a high-energetic vibratory mill. X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller method were applied to characterize the milled powders. During the thermal treatment at 1200 and 1400 °C in an argon atmosphere the nonstoichiometric CeO_2−x oxides with the defect fluorite structure were formed. Compositions of CeO_2−x oxides were determined according to its lattice parameter. The results showed that the release of oxygen, as well as the rate of reduction, was more effective in nanocrystalline then in the microcrystalline CeO₂, producing at 1200 °C CeO_1.80 and CeO_1.85 oxides, while at 1400 °C were obtained similarly, CeO_1.77 and CeO_1.78, compositions.     

Structure characterization and mechanical properties of CeO2–ZrO2 solid solution system

The measured and calculated lattice parameters, microstructures, and mechanical properties (fracture toughness and microhardness) of CeO₂–ZrO₂ system ceramics are investigated, using CeO₂–ZrO₂ solid solution powder prepared by a microwave-induced combustion process. The CeO₂–ZrO₂ solid solution ceramics were sintered at 1500 °C for 6 h in air; the density of all specimens was greater than 94% of the theoretical density. For Ce_1−xZr_xO₂ (0.00  x  0.50), the measured lattice parameter is in accordance with that of Kim's doped CeO₂ model_. On the other hand, for x  0.50, the measured values fit Kim's doped ZrO₂ model. The fracture toughness and microhardness of CeO₂–ZrO₂ system ceramics with various compositions were investigated with Vickers indentation. The results showed that the crack mode of CeO₂–ZrO₂ solid solution was Palmqvist cracks under loads of 1 kg. Generally, the fracture toughness should increase with grain size at the submicron scale. However, larger grains may lead to spontaneous transformation, which should decrease the potential toughening at room temperature. This behavior was observed in the Ce_0.25Zr_0.75O₂ ceramic, which demonstrated a high fracture toughness that may be ascribed to two causes: (1) fine grain size and (2) transformation toughening.     

Effect of CeO2 addition on densification and microstructure of Al2O3-YSZ composites

Alumina (Al₂O₃) and alumina-yttria stabilized zirconia (YSZ) composites containing 3 and 5 mass% ceria (CeO₂) were prepared by spark plasma sintering (SPS) at temperatures of 1350-1400 °C for 300 s under a pressure of 40 MPa. Densification, microstructure and mechanical properties of the Al₂O₃ based composites were investigated. Fully dense composites with a relative density of approximately 99% were obtained. The grain growth of alumina was inhibited significantly by the addition of 10 vol% zirconia, and formation of elongated CeAl₁₁O₁₈ grains was observed in the ceria containing composites sintered at 1400 °C. Al₂O₃-YSZ composites without CeO₂ had higher hardness than monolithic Al₂O₃ sintered body and the hardness of Al₂O₃-YSZ composites decreased from 20.3 GPa to 18.5 GPa when the content of ZrO₂ increased from 10 to 30 vol%. The fracture toughness of Al₂O₃ increased from 2.8 MPa m^1/2 to 5.6 MPa m^1/2 with the addition of 10 vol% YSZ, and further addition resulted in higher fracture toughness values. The highest value of fracture toughness, 6.2 MPa m^1/2, was achieved with the addition of 30 vol% YSZ.     

Synthesis and characterization of CeO2 nano-rods

We report a synthesis of two types of CeO₂ nano-rods via the facile and efficient hydrothermal process free from any surfactant and template. The synthesized nano-rods are chemically identified as CeO₂ with the standard fluorite structure but their morphologies are different. The nano-rods prepared with cerium nitrate hexahydrate and sodium phosphate are thicker and shorter with diameter of ∼30 nm and length of ∼100 nm, and those prepared with cerium acetate hydrate and dibasic sodium phosphate are thinner and longer with ∼10 nm in diameter and ∼400 nm in length. Microstructural analyses reveal that the two species of nano-rods have low-energy {111} surfaces and grow along the 〈112〉 direction. As a consequence of their morphologies, the two types of synthesized nano-rods exhibit excellent UV-absorption ability in comparison to the irregular CeO₂ nanoparticles.     

Investigation on mechanochemical synthesis of Al2O3/BN nanocomposite by aluminothermic reaction

Alpha-alumina–boron nitride (α-Al₂O₃–BN) nanocomposite was synthesized using mixtures of aluminum nitride, boron oxide and pure aluminum as raw materials via mechanochemical process under a low pressure of nitrogen gas (0.5 MPa). The phase transformation and structural evaluation during mechanochemical process were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential thermal analysis (DTA) techniques. The results indicated that high exothermic reaction of Al–B₂O₃ systems under the nitrogen pressure produced alumina, aluminum nitride (AlN), and aluminum oxynitride (Al₅O₆N) depending on the Al value and milling time, but no trace of boron nitride (BN) phases could be identified. On the other hand, AlN addition as a solid nitrogen source was effective in fabricating in-situ BN phase after 4 h milling process. In Al–B₂O₃–AlN system, the aluminothermic reaction provided sufficient heat for activating reaction between B₂O₃ and AlN to form BN compound. DTA analysis results showed that by increasing the activation time to 3 h, the temperature of both thermite and synthesis reactions significantly decreased and occurred as a one-step reaction. SEM and TEM observations confirmed that the range of particle size was within 100 nm.     

Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P

TiO₂- and CeO₂-promoted bulk Ni₂P catalysts were prepared by impregnation and in-situ H₂ temperature-programmed reduction method. The prepared catalysts were characterized by XRD and XPS. The hydrogenation activities of the catalysts were studied using 1.5 wt.% 1-heptene in toluene and 1.0 wt.% phenylacetylene in ethanol as the model feeds. The results indicate that bulk Ni₂P possesses low hydrogenation activity but is tunable by simply controlling the content of the additives (TiO₂ or CeO₂), suggesting that TiO₂ and CeO₂ are effective promoters to enhance the hydrogenation activity of Ni₂P.     

Directionally solidified CeO2 (or GDC)/CoO eutectic ceramics as cermet precursors for SOFCs anodes: Microstructure cross-over

Rods of CeO₂ and gadolinium-doped CeO₂ (GDC)-CoO eutectics were prepared by directional solidification using a laser heated floating zone (LFZ) technique. The microstructure has been studied as a function of the growth rate from V = 10 to 750 mm/h. Regular eutectic microstructures are obtained except for the highest growth rate. The interspacing follows the λ²V = C law with C = 4.1(3) × 10⁻¹⁷ and 2.6(3) × 10⁻¹⁷ m³/s for CeO₂-CoO and GDC-CoO eutectics, respectively. A cross-over between fibrous and lamellar eutectic microstructures was observed depending on the growth rate. The crystallography of the eutectics was studied by Electron Backscatter Diffraction (EBSD). The growth directions [1 1 0]_GDC ∼ //[110]_CoO, and the interfacial planes (200)_GDC//(111)_CoO, were identified. Solubility of Co in the ceria matrix was determined by Energy Dispersive X-ray (EDX) Spectroscopy after Co was leached out from the matrix. Co solubility in ceria at 1650 °C was found to be less than 1 mol%.     

Synthesis and electrochemical properties of CeO2 nanoparticle modified TiO2 nanotube arrays

In this paper, a cerium dioxide (CeO₂) modified titanium dioxide (TiO₂) nanotube array film was fabricated by electrodeposition of CeO₂ nanoparticles onto an anodized TiO₂ nanotube array. The structural investigation by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicated that the CeO₂ nanoparticles grew uniformly on the walls of the TiO₂ nanotubes. The composite was composed of cubic-phase CeO₂ crystallites and anatase-phase TiO₂ after annealing at 450 °C. The cyclic voltammetry and chronoamperometric charge/discharge measurement results indicated that the CeO₂ modification obviously increased the charge storage capacity of the TiO₂ nanotubes. The charge transfer process at the surface, that is, the pseudocapacitance, was the dominate mechanism of the charge storage in CeO₂-modified TiO₂ nanotubes. The greater number of surface active sites resulting from uniform application of the CeO₂ nanoparticles to the well-aligned TiO₂ nanotubes contributed to the enhancement of the charge storage density.     

Mechanical properties of plasma sprayed nanostructured TiO2 coatings on mild steel

This paper discusses the effects of plasma spray parameters on the mechanical properties of nanostructured TiO₂ coatings deposited on mild steel substrates. The design of experiment method was applied to investigate the significant effects of each property and to optimize the operational spray parameters. Plasma power, powder feed rate, and stand-off distance were selected as independent variables. Agglomerated and sintered nano-TiO₂ powder was deposited on A-36 commercial mild steel. The microstructural and mechanical properties of the coatings such as porosity, microhardness, surface roughness, and wear rate were evaluated. Both plasma power and powder feed rate were found to be the main factors affecting all four responses. It was also noted that the stand-off distance was a significant factor mainly in influencing the surface roughness of the coatings. All in all, the optimized properties can be achieved by applying a plasma power of 30 KW (high level), a powder feed rate of 22 g/min (high level), and a stand-off distance of 80 mm (low level).     

Fabrication of novel multilayer Al2O3-(m-ZrO2)/t-ZrO2 fibrous ceramics composites

A novel layered microstructure in the Al₂O₃/ZrO₂ composites system was fabricated by the multipass extrusion method. The microstructure consisted with very fine alternate lamina of Al₂O₃-(m-ZrO₂) and t-ZrO₂. The composites were designed in such a way that a small group of 7 cylindrical alternate layers of Al₂O₃-(m-ZrO₂) and t-ZrO₂ made a concentric microgroup around 40 μm in diameter, with a common boundary layer between the adjacent groups. The thickness of both layers was around 2-3 μm. The microstructure was unidirectionally aligned throughout the composites. The composite microstructure was fibrous due to the unidirectional orientation of these microgroups. Detailed microstructure of the fabricated composites was characterized by SEM. The effect of the concentric layered microstructure on mechanical behavior was discussed. Material properties such as density, bending strength, Vickers hardness and fracture toughness were measured and evaluated depending on different sintering temperatures.     

Synthesis of CeO2-ZrO2 solid solution by glycothermal method and its oxygen release capacity

The glycothermal (GT) reaction of Ce acetate and Zr alkoxide directly yielded CeO₂-ZrO₂ solid solutions in a region of low Ce content ≤40 mol%. Of the CeO₂-ZrO₂ solid solutions obtained by the GT method and subsequent calcination at 500 or 800 °C, the sample with 20 mol% Ce content had the largest BET surface area. This sample exhibited the highest Ce-based oxygen release capacity in the whole Ce/Zr composition range. The oxygen release capacities of CeO₂-ZrO₂ solid solutions synthesized by the GT method were much larger than those of the samples prepared by a coprecipitation (CP) method. The Reitveld analysis and the repetitive reduction-oxidation experiment indicated that the CeO₂-ZrO₂ solid solution synthesized by the GT method has a homogeneous structure as compared with that prepared by the CP method.     

Microwave dielectric properties of SnO2-doped CaSiO3 ceramics

SnO₂-doped CaSiO₃ ceramics were successfully synthesized by a solid-state method. Effects of different SnO₂ additions on the sintering behavior, microstructure and dielectric properties of Ca(Sn_1−xSi_x)O₃ (x=0.5–1.0) ceramics have been investigated. SnO₂ improved the densification process and expanded the sintering temperature range effectively. Moreover, Sn⁴⁺ substituting for Si⁴⁺ sites leads to the emergence of Ca₃SnSi₂O₉ phase, which has a positive effect on the dielectric properties of CaO–SiO₂–SnO₂ materials, especially the Qf value. The Ca(Sn_0.1Si_0.9)O₃ ceramics sintered at 1375 °C possessed good microwave dielectric properties: ε_r =7.92, Qf =58,000 GHz and τ_f=−42 ppm/°C. The Ca(Sn_0.4Si_0.6)O₃ ceramics sintered at 1450 °C also exhibited good microwave dielectric properties of ε_r=9.27, Qf=63,000 GHz, and τ_f=−52 ppm/°C. Thus, they are promising candidate materials for millimeter-wave devices.     

Sintering of Al2O3-SiC composite from sol-gel method with MgO, TiO2 and Y2O3 addition

Al₂O₃-SiC composite ceramics were prepared by pressureless sintering with and without the addition of MgO, TiO₂ and Y₂O₃ as sintering aids. The effects of these compositional variables on final density and hardness were investigated. In the present article at first α-Al₂O₃ and β-SiC nano powders have been synthesized by sol-gel method separately by using AlCl₃, TEOS and saccharose as precursors. Pressureless sintering was carried out in nitrogen atmosphere at 1600 °C and 1630 °C. The addition of 5 vol.% SiC to Al₂O₃ hindered densification. In contrast, the addition of nano MgO and nano TiO₂ to Al₂O₃-5 vol.% SiC composites improved densification but Y₂O₃ did not have positive effect on sintering. Maximum density (97%) was achieved at 1630 °C. Vickers hardness was 17.7 GPa after sintering at 1630 °C. SEM revealed that the SiC particles were well distributed throughout the composite microstructures. The precursors and the resultant powders were characterized by XRD, STA and SEM.     

Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.     

Autothermal reforming of ethanol for hydrogen production over an Rh/CeO2 catalyst

Hydrogen production from ethanol by autothermal reforming over an Rh/CeO₂ catalyst was investigated with a stoichiometric feed composition. Ethanol as well as the reaction intermediates like acetaldehyde and acetone was entirely converted to hydrogen and C1 products at 673 K, and methane steam reforming and reverse water gas shift were the major reactions above 823 K. The Rh/CeO₂ catalyst exhibited stable activity and selectivity during 70 h on-stream operation at 823–923 K without obvious deactivation evidenced by the constant effluent gas composition. Structural analysis of the used catalyst revealed that CeO₂ prevented effectively the highly dispersed Rh particles with sizes of 1–3 nm from sintering and thus maintained sufficient Rh–CeO₂ interfacial areas, which facilitated coke gasification through the high oxygen storage-release capacity.     

TiO2 as a sintering additive for KNbO3 ceramics

Improved densification during the conventional sintering of KNbO₃ ceramics was achieved by using small additions of TiO₂. This improved densification can be explained on the basis of high-temperature chemical reactions in the system. X-ray diffractometry and electron microscopy were used in combination with diffusion-couple experiments in order to elucidate the chemical reactions between KNbO₃ and TiO₂. TiO₂ reacts with KNbO₃ forming KNbTiO₅, and a low concentration of Ti incorporates in the KNbO₃ structure resulting in the formation of oxygen vacancies and, consequently, in an improvement in the densification. At ∼1037 °C eutectic melting between the KNbO₃ and the KNbTiO₅ further improves the densification of the KNbO₃ ceramics.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Approach of phase transformations and densification in nanostructured and (Bi2O3, ZnO,TiO2) doped silica ceramics

The low temperature sintering of silica is studied under the influence of sintering aids and nanosized powders using X-Ray Diffractometry (XRD) and high-temperature environmental scanning electron microscopy analyses (HT-ESEM). Two particular aids were chosen to conduct this study, [Bi₂O₃–ZnO]_eutectic and titania. We report a lowering of the crystallization temperature when the former compound is introduced in the silica while a raise is observed when the latter is used. Moreover, the amorphous silica crystallization into cristobalite inhibits drastically the kinetics of densification of silica-based materials.     

Synthesis and electrochemiluminescence of the CeO2/TiO2 composite

CeO₂/TiO₂ composite with kernel–shell structure was synthesized by a sol–gel process. The characterization results show that the composite is made up of anatase phase TiO₂ and cubic system CeO₂. The electrochemiluminescence (ECL) behavior of the CeO₂/TiO₂ composite was studied by a cyclic voltammetry in the presence of persulfate, and the effect factors on ECL emission were discussed. Based on a series of experiments, it is proposed that the strong dual ECL emission produced by the CeO₂/TiO₂ composite resulted from the benefit ECL effect of interface heterojunction in composite.