Papers by Author: Masahiko Demura

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: 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 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.

Abstract: The catalytic activity of oxidation-reduction pre-treated Ni3Al powder for methane steam reforming was examined. The oxidation-reduction pre-treatment consisted of two steps: oxidation in air at various temperatures from 973 to 1373 K, and then followed by reduction in H2 at 873 K. It was found that the oxidation-reduction treatments significantly reduced the onset temperature of activity, i.e., improved the activity of Ni3Al powder at low temperatures. The characterization of Ni3Al surface showed that an outer surface layer of fine NiO particles were formed on the surface of Ni3Al after oxidation. These NiO particles were reduced to metallic Ni by the subsequent reduction treatment, resulting in the high activity for methane steam reforming. These results indicate that the Ni3Al can form highly active surface structure with oxidation-reduction treatment, having excellent heat resistance.

Abstract: Evolution of surface morphology in Ni(γ)/Ni3Al(γ´) two-phase foil of binary Ni-18 at.%Al was examined during the electrochemically selective etching in the electrolyte of distilled water including 1 wt.% (NH4)2SO4 and 1 wt.% citric acid. In the early stage (0.5 h), only the γ matrix was etched and the outmost γ´ particles were protected by a preexisting surface product. As the γ matrix was etched more, the side surfaces of the outmost γ´ particles and the γ´ particles that were located inside were exposed in the electrolyte. They were dissolved, and had a high density of fine dimples. However, the dissolution rate of the γ´ particles was slower than that of the γ matrix and thus the selective etching was retained in this stage. Finally, at 5h, more γ´ particles were exposed and the flat and smooth surfaces of the outmost γ´ particles were completely eliminated by the dissolution on the side surfaces. From these observations plus the saturation of the current density observed in the electrochemical test, we concluded that the change in the surface morphology was finished at this stage. Thus, the surface became more rough and irregular, which resulted from the original two-phase microstructure and the fine dimple structure by transpassivation.

Abstract: Primary recrystallization textures were examined in the 84% and 95% cold-rolled boron-free Ni3Al single crystals with a Goss texture using the electron backscatter diffraction method. It was found that the main components of the textures in the specimens heat-treated at 873K/0.5h had a 40° rotation relationship about <111> to the original, Goss texture. All the eight variants of 40°<111> rotated grains existed. However, the number density is not even but dependent on whether the rotation axis is identical to the normal of slip planes activated during the prior cold rolling. The ratio of the number density among the variants was same in both the 84% and 95% cold-rolled foils. Based on these results, the formation of these 40°<111> rotated grains was explained assuming the modified multiple twinning mechanism where the annealing twinning occurred at the activated slip planes, followed by the subsequent twinning.