Papers by Author: Toshiyuki Hirano

Abstract: The catalytic activity of Ni-Al (Ni25Al) nanoparticles fabricated by thermal plasma evaporation was examined for methanol decomposition and CO oxidation. The nanoparticles exhibited high activity for both reactions. Characterization of the nanoparticles revealed that the fabricated nanoparticles were mainly comprised of Ni and Ni₃Al phases. During CO oxidation, the Ni phase was oxidized to NiO, while the Ni₃Al phase remained unchanged. The NiO phase is supposed to serve as the active sites for CO oxidation. In contrast, during methanol decomposition, no obvious oxidation was observed for both Ni and Ni₃Al phases. The Ni and Ni₃Al phases are supposed to contribute to the high activity for methanol decomposition.

Abstract: The activated slip systems were analyzed in the cold rolling of a Ni₃Al single crystal with an initial orientation of ~[-112](512), which showed an irregular rolling deformation, i.e. widening, bending, and shear deformation. A phenomenological crystal plasticity model was applied using a spectral method. The boundary condition was optimized to reproduce the actual rolling deformation, as follows. That is, the orthogonal components of the deformation gradient were given from the measured widening and reduction, and the shear components were iteratively optimized as to that the final orientation was as close to the experimental one as possible. The calculated result showed that three slip systems, a3, b1, and d1 in the Bishop-Hill notation, were mainly activated in the irregular rolling deformation, which result was consistent to the previous observation of the slip traces [Kishida et al., Philos. Mag. 83 (2003) 3029]. The three activated systems were identical to those activated in the plane-strain condition. However, the quantitative comparison revealed that the activity of b1 was significantly reduced in the irregular rolling deformation, while the activity of d1 was enhanced instead. The less activity of b1 and the enhancement of d1 can be understood assuming a strong interaction between a3 and b1. The reaction of this pair has been reported to form the superlattice intrinsic stacking fault (SISF) in Ni₃Al [Chiba and Hanada, Philos. Mag. A. 69 (1994) 751]. It is likely that the formation of the SISF, which are considered immobile in Ni₃Al, restrained the activation of b1, leading to the irregular rolling deformation.

Abstract: The effect of acid and alkali leaching on catalytic activity of an atomized Ni₃Al powder for methanol decomposition was investigated. It was found that a two-step process, an acid leaching followed by an alkali leaching, was most effective for improving the activity. The optimal conditions of acid and alkali leaching were examined. The effect of the acid and alkali leaching was attributed to the formation of fine Ni species and a porous surface structure.

Abstract: Notch effect on the fracture behavior of the Ni3Al foils has been investigated as a function of notch radius and depth. Tensile tests along the rolling direction showed that notch weakening occurred with introduce of notch. The effective stress concentration factor (ke) was much lower than the theoretical stress concentration factor (Kt), which was due to the local plastic deformation at the notch root. Cracks initiated along the shear band in the RD tension.

Abstract: The objective of this study is to investigate the catalytic properties of intermetallic Ni₃Fe foil. We fabricated Ni₃Fe foil of 30 µm in thickness by a metallurgical process, and examined the catalytic activity of the Ni₃Fe foil for methanol decomposition from 513 to 973 K. The Ni₃Fe foil showed activity for methanol decomposition above 623 K. The activity increased with the increase of reaction temperature. Surface analysis revealed that a surface structure of fine Ni-Fe particles dispersed on carbon nanofibers was formed on the foil during the reaction. The activity is attributed to the formation of this fine structure.

Abstract: The catalytic properties of the cold-rolled foils of intermetallic compound TiNi were studied for hydrogen production from methanol in a temperature range of 513-793 K. The catalytic activity for methanol decomposition increased with a reaction temperature, especially above 673 K. The SEM and EDS analyses revealed the formation of numerous Ni-enriched particles dispersed in the layer of carbon fibers during the reaction. The catalytic activity of TiNi foils is attributed to those Ni-enriched particles.

Abstract: This paper presents the characteristic features of the catalytic properties of the cold-rolled Ni₃Al foils for methanol decomposition which were developed in our group. Methanol was effectively decomposed into H₂ and CO over the foils above 713 K. The production rates of H₂ and CO increased with an increase of time during the initial period of reaction, indicating that the Ni₃Al foils were spontaneously activated under the reaction conditions. Surface analyses revealed that fine Ni particles dispersed on carbon nanofibers formed on the foils during the reaction. The high catalytic performance of the foils can be attributed to the spontaneous formation of this nanostructure during the reaction.

Abstract: This article presents the texture evolution and the ductility improvement of the cold-rolled foils of boron-free Ni₃Al during the recrystallization and the subsequent grain growth. The cold-rolled foils had sharp {110} textures. After the recrystallization at 873K/0.5h, the texture was disintegrated with several texture components. Interestingly, most of them had a single rotation relationship. i.e. 40˚ around <111>. With the progress of the grain growth, however, the texture returned to the sharp, cold-rolled textures. This two-stage texture evolution, called as “Texture memory effect”, was explained assuming a high mobility of the grain boundary with the 40˚<111> rotation relationship. The texture returning was highly effective to improve the ductility of the foils.

Abstract: In order to pursue high catalytic performance of Ni-Al intermetallic compounds for hydrogen production, we synthesized Ni-Al intermetallic nanoparticles from Ni-Al alloy ingots by vacuum arc plasma evaporation technique for the first time. The characterization of the synthesized nanoparticles was carried out using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy. The catalytic properties of the Ni-Al nanoparticles for methanol decomposition were evaluated. It is found that the nanoparticles had a large surface area above 70 m2/g, and showed very high catalytic activity for methanol decomposition.

Abstract: Texture evolution during recrystallization and grain growth was examined for a Ni3Al/Ni two-phase single crystal (binary Ni-18 at.% Al) 83% cold-rolled, then compared with that for a Ni3Al single-phase single crystal (Ni-24 at.% Al). The cold-rolled single crystal had a sharp {110}<001> (Goss) texture. When it was recrystallized at 873K, the texture changed into a complicated one consisting of several components. Most of them had a special rotation relationship to the original Goss texture, i.e. 40˚ about <111>, which special relationship was similarly observed in the single-phase case. The 40˚<111> texture became shaper with no quantitative change as the grain growth proceeded. This high stability of the recrystallized texture contrasted with the single-phase case in which the authors previously found that the texture returned to the original Goss texture. The difference was discussed based on the orientation analysis by an electron backscattered diffraction method.