A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

About the Method of Thermoreactive Electrospark Surface Strengthening

The method of Thermoreactive Electrospark Surface Strengthening (TRESS) is presented in this work. Thus the process of coating formation becomes a less energy consuming one as compared to the basic technology of the electrospark alloying. The additional heat of the chemical reaction of the synthesis final products formation on the substrate contribute to the increase of thickness and continuity of the coating, to the diminution of the inner tension due to the smoother concentration gradients through the coating thickness. The opportunities of TRESS method are exposed with the example of the FGM wear- and heat-resistant coating formation on the base of NiAl, TiAl. FGM diamond containing coatings production by the said method is presented. Optimal conditions and technological parameters for diamond containing coatings deposition is found. The masstransfer kinetics, the coating structure and properties were studied.     

Room-temperature miscibility gap in LixFePO4

The rechargeable lithium-ion cell is an advanced energy-storage system. However, high cost, safety hazards, and chemical instability prohibit its use in large-scale applications. An alternative cathode material, LiFePO(4), solves these problems, but has a kinetic problem involving strong electron/hole localization. One reason for this is believed to be the limited carrier density in the fixed monovalent Fe(3+)PO(4)/LiFe(2+)PO(4) two-phase electrode reaction in LixFePO4. Here, we provide experimental evidence that LixFePO4, at room temperature, can be described as a mixture of the Fe(3+)/Fe(2+) mixed-valent intermediate LialphaFePO4 and Li1-betaFePO4 phases. Using powder neutron diffraction, the site occupancy numbers for lithium in each phase were refined to be alpha=0.05 and 1-beta=0.89. The corresponding solid solution ranges outside the miscibility gap (0相似文献   

Selective dissolution of nanolamellar Ti–41 at.% Al alloy single crystals

The selective dissolution behavior of Ti–41 at.% Al single crystals having a α₂/γ-lamellar structure with a lamellar thickness in the range 20 nm to 1 μm have been investigated in 0.5 M NaCl aqueous solution focusing on the effect of lamellar thickness on the dissolution of γ-lamellae. In the case where γ-lamellae were thicker than ～100 nm on average, γ-lamellae were selectively dissolved and, as a result, crevasses whose widths were close to the γ-lamellae thicknesses were formed. However, not all γ-lamellae were dissolved and the distribution of crevasses was much less uniform compared with that of the γ-lamellae. On the other hand, when the average γ-lamellae thickness was <100 nm relatively thick γ-lamellae were preferentially dissolved, but the distribution of the crevasses was relatively uniform compared with that obtained from the coarse lamellar structure. The reasons for this difference are discussed from the viewpoint of the absence of misfit dislocations in nanoscaled lamellae and the difference in ion transport through crevasses of different width formed by dissolution of γ-lamellae.     

Dissolution behavior of irradiated mixed oxide fuel with short stroke shearing for fast reactor reprocessing

An efficient dissolution process was established for future reprocessing in which mixed-oxide (MOX) fuels with high plutonium contents and dissolver solution with high heavy-metal (HM) concentrations (more than 500 g dm^?3) will be treated. This dissolution process involves short stroke shearing of fuels (～10 mm in length). The dissolution kinetics of irradiated MOX fuels and the effects of the Pu content, HM concentration, and fuel form on the dissolution rate were investigated. Irradiated fuel was found to dissolve as 10²–10³ times fast as non-irradiated fuel, but the rate decreased with increasing Pu content. Kinetic analysis based on the fragmentation model, which considers the penetration and diffusion of nitric acid through fuel matrices prior to chemical reaction, indicated that the dissolution rate of irradiated fuel was affected not only by the volume ratio of liquid to solid (L/S ratio) but also by the exposed surface area per unit mole of nitric acid (A/m ratio). The penetration rate of nitric acid is expected to be decreased at high HM concentrations by a reduction in the L/S ratio, but enhanced by shearing the fuel pieces with short strokes and thus enlarging the A/m ratio.     

Fermentation Process and Grain Structure of Baked Breads from Frozen Dough Using Freeze-Tolerant Yeasts

The fermentation process for frozen doughs using freeze‐sensitive (Saccharomyces cerevisiae, Kyowa for sweet bread; S. cerevisiae, FC for white bread) and freeze‐tolerant (S. cerevisiae, YF for sweet bread) yeasts was traced by magnetic resonance imaging (MRI). Grain network structures of baked breads were also visualized by MRI. Prefermentation before freezing, punching and remolding, or resheeting and molding treatments increased loaf volume by 10 to 110% for the baked breads using freeze‐tolerant yeast, while these treatments decreased loaf volume by 70% using freeze‐sensitive yeast. The first fermentation before freezing and the second fermentation with punching or resheeting after thawing are useful for obtaining good quality breads from frozen dough using freeze‐tolerant yeast.     

Syntheses of hollandite type Rb2Cr8O16, K2Cr2V6O16 and K2V8O16

Hollandite-type compounds, Rb₂Cr₈O₁₆, K₂Cr₂V₆O₁₆ and K₂V₈O₁₆, were synthesized under high P-T conditions up to 1200°C and 7GPa. The structural refinement using a single crystal of Rb₂Cr₈O₁₆ confirms that the structure is similar to that of K₂Cr₈O₁₆. Magnetic measurements indicate that Rb₂Cr₈O₁₆ is ferromagnetic below 295K, K₂Cr₂V₆O₁₆ paramagnetic down to 77K and K₂V₈O₁₆ has susceptibility anomaly at 175K. These compounds are all semiconductive and show discontinuities in temperature-resistivity curves at points corresponding to magnetic anomalies.     

Five percent break BWR LOCA/ECC test at ROSA-III without HPCS actuation - two-dimensional core thermal-hydraulic phenomena

The ROSA (Rig of Safety Assessment)-III facility is a volumetrically scaled (1/424) simulated boiling water nuclear reactor (BWR) system with an electrically heated core designed for integral loss-of-coolant accident (LOCA) and emergency core cooling system (ECCS) tests. A recirculation pump suction line break test with a five percent break area was conducted with the assumption of high pressure core spray system (HPCS) failure. The simulated peripheral fuel rods facing the channel box wall had a tendency to be rewetted temporarily at the upper part of the core by falling water from the upper plenum before low pressure core spray system (LPCS) actuation, while the rods in the central region were not rewetted but quenched mainly from the bottom of the core after low pressure coolant injection system (LPCI) actuation. Therefore, the peak cladding temperatures of the simulated high power fuel rods were limited to lower values since they were located in the peripheral region and the temporary rewetting before LPCS actuation occurred mainly in the peripheral region. The ROSA-III five percent break test and a BWR counterpart were analyzed with the RELAP5/MOD1 (cycle 018) code. Similarity between the ROSA-III small break test and a BWR small break LOCA has been confirmed through comparison of the calculated results.     

Sub-boundaries in3He and4He single crystal and their migration below 1K observed by X-ray topography

The observation of alterations in crystal structure at ultra-low temperatures by X-ray diffraction, made possible by the realization of synchrotron radiation use after a quarter of this century, plays an important role in obtaining an understanding of the base structure of solids. For that, two types of³He-⁴He dilution refrigerators with a modified version of the top-loading facilities were installed at the BL-3C₂ and 6C₁ stations of the Photon Factory. In BL-3C₂, the behaviors of lattice defects in solid helium have been studied by X-ray topography. In this note, the migrations of sub-boundaries in³He and⁴He single-crystals are reported as being the result of an annealing effect. After annealing hcp⁴He single crystals for 80min at 0.5K, no change in crystallographic orientations could be easily observed from white SR X-ray topographs. In the same type topographs of bcc³He single crystals after annealing for several hours at 03K, migration of sub-boundaries were conspicuously discerned.