Effect of CaO–ZrO2 addition to Ni supported on γ-Al2O3 by sequential impregnation in steam methane reforming

Ni catalysts supported on (CaO–ZrO₂)-modified γ-Al₂O₃ were prepared by sequential impregnation. The effects of varied CaO to ZrO₂ mole ratios at 0, 0.20, 0.35, 0.45, and 0.55 on the activity and stability of the modified Ni catalysts were studied. As a result of using CaO–ZrO₂ as a promoter, each catalyst contained CaO–ZrO₂ at only 5%. γ-Al₂O₃ used as support was modified by CaO–ZrO₂ before the deposition of nickel oxide. The addition of CaO–ZrO₂ at an optimum ratio was expected to improve the stability of Ni catalysts due to the decrease of carbon formation resulting from carbon gasification. All the fresh catalysts were characterized by ICP, XRD, BET surface area, TGA in H₂, and TPR before catalytic testing in steam methane reforming at 600 °C. The spent catalysts were examined by TEM and TGA to observe the catalysts deactivation. The identification of CaO–ZrO₂ phases indicated that CaO and ZrO₂ reacted with each other to be monoclinic solid solution ZrO₂, CaZr₄O₉, CaZrO₃, and CaO corresponding to the phase diagram of CaO–ZrO₂. The existence of CaZrO₃ for 0.55 mol ratio of CaO/ZrO₂ enhanced activity in steam methane reforming because oxygen vacancies in CaZrO₃ greatly preferred the water adsorption creating the favorable conditions for carbon gasification and, then, water gas shift. The prominence and continued existence of these two reactions on the Ni catalysts leads to the particular increase of H₂ yield. Moreover, the increasing amount of CaZrO₃ in the Ni catalysts significantly improved carbon gasification. However, the Ni catalysts with CaZrO₃ showed whisker carbon after catalytic testing; this carbon specie has not been tolerated in steam methane reforming. Therefore, these results significantly differed from the hypothesis.     

Numerical analysis of residual stress distribution generated by welding after surface machining based on hardness variation in surface machined layer due to welding thermal cycle

Recently, stress corrosion cracking (SCC) has been observed near the welded zone of the primary loop recirculation pipes made of low-carbon austenitic stainless steel type 316L in boiling water reactors. SCC is initiated by superposition effect of three factors. They are material, environmental and mechanical factors. For non-sensitized material such as type 316L, residual stress as a mechanical factor of SCC is comparatively important. In the joining processes of pipes, butt welding is conducted after surface machining. Surface machining is performed in order to match the inside diameter and smooth surface finish of pipes. Residual stress is generated by both processes. Moreover, residual stress distribution generated by surface machining is varied by subsequent welding processes, and it has the maximum residual stress around 900 MPa near the weld metal. The variation of metallographic structure, such as recovery and recrystallization, in the surface machined layer due to the welding thermal cycle is an important factor for this residual stress distribution. In this study, thermal ageing tests were performed in order to evaluate hardness variation due to the thermal cycle in the surface machined layer. Results of thermal ageing tests were applied to the finite-element method as the additivity rule of the hardness variation. Varied hardness was converted into equivalent plastic strain. Then, thermo-elastic-plastic analysis was performed under residual stress fields generated by surface machining. As a result, analytical results of surface residual stress distribution generated by bead-on-plate welding after surface machining show good agreement with measured results by the X-ray diffraction method. The maximum residual stress near the weld metal is generated by the same mechanism as in the both-ends-fixed bar model in the surface machined layer that has high yield stress.     

Application of alkali metal-doped carbons for hydrogen recovery and isotope separation

Hydrogen-sorption isotherms of alkali metal-doped carbons at 77 K were determined for promoting application of these materials as hydrogen-recovery and isotope-separation agent. The hydrogen-sorption behavior of rubidium-doped Grafoil, with composition of RbC24, showed high sorption ability against hydrogen at low pressure. Taking into account the fact that sorption-desorption was fast and reversible, and the equilibrium pressure at half coverage was very low, i.e., 40 Pa, RbC24 prepared from Grafoil is promising as a recovery agent for hydrogen gas at low pressure. The hydrogen (H2)/deuterium(D2)-sorption isotherms of potassium-doped carbons with composition of KC10, prepared from multi wall carbon nanotube (MWCNT) and carbons derived from petroleum cokes with heat-treatment temperatures of 1000 and 1500 degrees C, were also determined. Isotope separation coefficient was estimated from those isotherms. A very large isotope effect was found for KC10 prepared from MWCNT, comparable to those prepared from carbons with heat-treatment temperatures of 1000 or 1500 degrees C. However, a severe problem was found for KC10 (MWCNT) that repetition of the sorption-desorption cycles resulted in the decrease of the sorbed amount of H2 and D2.     

Magnetic Field Effect on Chemical Compositions of Magnetic Aerosol Particles Synthesized Photochemically from a Gaseous Mixture of Iron Pentacarbonyl and Trimethylsilyl Azide

Under intense UV light irradiation with an Nd:YAG laser at 355 nm, a gaseous mixture of iron pentacarbonyl (Fe(CO)₅) and trimethylsilyl azide (TMSAz) produced aerosol magnetic particles with diameters of 50–100 nm. Two photon absorption of TMSAz and Fe(CO)₅ took place efficiently to produce trimethylsilyl nitrene and iron carbonyls (Fe(CO) _n n = 1–4). In cases where a partial pressure of TMSAz was high, nucleation reactions of aerosol particles proceeded via chemical reactions between trimethylsilyl nitrene and two iron carbonyls, resulting in bridging between two iron carbonyls by silyl nitrene. In cases where a partial pressure of TMSAz was low, the nucleation reactions proceeded via chemical reactions between two iron carbonyls, resulting in the formation of di-iron carbonyls with bridging >C?O group. Both of these nucleation reactions took place concurrently during aerosol particle formation. From FT-IR spectral change of sedimentary particles produced under an external magnetic field of up to 5 T, it was found that application of an external magnetic field accelerated the latter chemical reaction to result in the appearance of bridging ν(>C?O) band in FT-IR spectrum of the magnetic particles.

Copyright 2013 American Association for Aerosol Research     

Thermal conduction theoretical analysis of temperature distribution during multiple-electrode submerged arc welding

In recent years, in order to reduce the costs of transportation and construction of pipelines, which are often constructed using multiple-electrode submerged arc welding (SAW), higher joint performance is required. Therefore, there has arisen the need to understand theoretically and control appropriately metallurgical and mechanical characteristics in heat-affected zone (HAZ), which has a significant influence on the strength and toughness of welded joints. Commonly, metallurgical phenomena in HAZ are evaluated based on the highest temperature and the cooling rate. Therefore, in order to control metallurgical and mechanical characteristics in HAZ by means of the welding conditions, evaluating the temperature distribution and the temperature history near the melted zone is essential. However, a detailed investigation of the temperature distribution for multiple-electrode SAW has not yet been carried out enough. In this study, in order to investigate the temperature distribution and histories during multiple-electrode SAW, the experimental results are compared with the theoretical results. In the theoretical analysis, the temperature rise equation in multiple heat sources welding is developed using the method of summation. Furthermore, on temperature distribution during welding, the effects of multiple heat sources, such as the number of heat sources and the distance between each electrodes, are considered quantitatively through the thermal conduction theoretical analysis. As the result, the distance between lead heat source and final heat source primally influences the area with the difference between a single heat source welding and multiple heat sources welding. Based on the results, it is expected to control temperature distribution near melted zone by more appropriate heat input characteristics, which is depended on heat source arrangement.     

Experimental study on relationship between heat parameter and angular distortion

It is well known that weld residual stress and distortion should be controlled appropriately for structural integrity. Recently, it has become much more necessary to control weld distortion to highly improve manufacturing efficiency. Various studies on control of weld distortion had been conducted based on clarification of influential dominant factors for that. The influential dominant factors had been studied from a viewpoint of temperature distribution in plate thickness section. Without considering moving the weld heat source, the temperature distribution is controlled by weld heat input (Q_net) per weld length. Angular distortion, which is controlled by temperature distribution along the direction of plate thickness (h), is controlled by heat input parameter (Q_net/h²). However, it has recently become known that the conventional results cannot be applied to all welding processes because such processes are becoming more diversified. It is significant for more accurate control of angular distortion to investigate once again the relationship between the heat input parameter and angular distortion. In this study, a series of experiments on the relationship between heat input parameter and angular distortion are carried out. The effects of welding current and welding speed are investigated individually in both TIG and MAG welding. The difference between these welding methods is also investigated. Based on the result, the effects of them are discussed in relation to temperature distribution during welding. It is considered that angular distortion is affected by temperature distribution not only in plate thickness section but also along welding direction. So, angular distortion is not always controlled by only the conventional heat input parameter because the heat input parameter is proposed as the influential dominant factor for temperature distribution in plate thickness section. It is concluded that generation characteristics of inherent strain should be considered in relation to three-dimensional temperature distributions during welding for more accurate control of angular distortion.     

High-velocity impact experiment of aluminum foam sample using powder gun

Porous materials such as aluminum foam have been investigated for possible use as impact shock absorbers in transportation aeronautic applications. However, the response of aluminum foam during impacts at high velocities of more than 100 m/s is not yet fully understood. A high-velocity impact experiment was therefore carried out to clarify impact shock absorption properties of aluminum foam. A one-stage powder gun was used to accelerate an aluminum foam sample to impact a rigid wall. Velocity and deformation of the aluminum foam sample during impact was studied using a digital high-speed video camera, while the pressure wave in the aluminum foam sample was measured using a PVDF gauge. The experimental observations revealed uneven collapse of the aluminum foam sample structure during high speed impact with a general stress plateau effect, typical for cellular material structures when subjected to quasi-static loading.     

Clinical characteristics of patients with rheumatoid arthritis and methotrexate induced pneumonitis

OBJECTIVE: To determine the clinical features of methotrexate (MTX) pneumonitis in patients treated for rheumatoid arthritis (RA). METHODS: The medical records of 284 patients with RA who had been treated with oral MTX (mean followup 33.2 mo) were reviewed retrospectively. RESULTS: MTX induced interstitial pneumonitis developed in 6 patients (2.1%). The affected patients were significantly older than those without MTX pneumonitis (67.3 +/- 9.8 vs 52.4 +/- 12.6 yrs, respectively; p < 0.005). The cumulative MTX dose ranged from 65 to 580 mg at the time pneumonitis developed. Five of the patients (83%) had preexisting interstitial abnormalities, while only 29 of the 278 patients without MTX pneumonitis (10%) had such abnormalities (p < 0.001). The frequency of adverse effects due to previous treatment with disease modifying antirheumatic drugs (DMARD) was 66.7% in MTX pneumonitis patients and 14.3% in the other 278 patients (p < 0.01). CONCLUSION: Advanced age, preexisting interstitial abnormalities, and previous adverse reactions to DMARD may be associated with MTX pneumonitis. Patients with these characteristics require careful monitoring during MTX therapy.     

Evolving neural networks with iterative learning scheme for associative memory

A locally iterative learning (LIL) rule is adapted to a model of the associative memory based on the evolving recurrent-type neural networks composed of growing neurons. There exist extremely different scale parameters of time, the individual learning time and the generation in evolution. This model allows us definite investigation on the interaction between learning and evolution. And the reinforcement of the robustness against the noise is also achieved in the evolutional scheme.