Papers by Author: Ryusuke Nakamura

Abstract: Formation behavior of nanovoids during the annealing of amorphous Al₂O₃ and WO₃ was studied by transmission electron microscopy. The density and size of the voids in Al₂O₃ and WO₃ increase with increasing annealing temperature from 973 to 1123 K and from 573 to 673 K, respectively. It is suggested that the formation of nanovoids during annealing is attributed to the large difference in density between as-deposited amorphous and crystalline oxides.

Abstract: The formation process of oxide nanotube via metal oxidation reaction was studied by transmission electron microscopy for Cu, Fe, and Ni nanowires. Cu2O and Fe3O4 nanotubes were formed after the oxidation of Cu and Fe nanowires with a diameter of 55 nm in air at 423 and 573 K for 3.6 ks, respectively. Both Cu2O and Fe3O4 nanotubes had a cylindrical interior pore with uniform diameter. On the other hand, Ni nanowires became bamboo-like structures of NiO with separate interior pores after oxidation at 673 K for 7.2 ks. The formation of the interior pores in Cu2O and Fe3O4 nanotubes and NiO bamboo-like structures can be explained by the rapid outward diffusion of metal ions through the oxide layers and the clustering of excess vacancies.

Abstract: Changes in morphology during the oxidation of iron nanoparticles and nanowires at 473~ 873 K have been studied by transmission electron microscopy. Iron nanoparticles and wires become hollow nanoparticles and nanotubes of Fe3O4 at temperatures below 673 K as a result of vacancy aggregation in the oxidation process. On the other hand, the hollow magnetite transforms into duplex porous structures with an interior nanopore and additional nanovoids at higher temperatures above 673 K, where the shrinkage of hollow nanoparticles and nanotubes starts and the phase transformation from Fe3O4 to -Fe2O3 occurs. Transition in porous structure seems to be related to the outward diffusion of vacancies from interior pore and the phase transformation in the shrinkage process.

Abstract: Reaction diffusion in liquid Pb free solder- and solid Pb free solder- pure Cu systems has been investigated in the temperature range between 397 K and 563 K. The Pb free solder of which composition is 95.7 mass% Sn, 2.8 mass% Ag, 1.0 mass% Bi and 0.5 mass% Cu and 99.99 mass% oxygen free Cu has been used. In the liquid Pb free solder-pure Cu system, as soon as the solder melted down, an intermetallic compound phase formed preferentially, and grew with increasing diffusion time. Only the phase exists in the experimental time up to 120 seconds. The layer thickness of the phase obeyed the parabolic law. On the other hand, in the solid Pb free solder-pure Cu system two intermetallic compounds  phase and ’ phase form and grew with increasing diffusion time, although the  phase forms after an incubation time at low temperature. The layer thickness of these intermetallic compounds obeyed the parabolic law. The growth rate of ’ phase is greater than that of the  phase. The growth kinetics of the intermetallic compounds and the diffusion behavior in the ’ phase have been investigated.

Abstract: The formation mechanisms of hollow metal oxide through the oxidation of several metal nanoparticles have been studied by transmission electron microscopy. For Zn, Al, Cu, Ni and Fe nanoparticles, hollow oxide nanoparticles were obtained as a result of vacancy aggregation in the oxidation processes. The formation of the hollow morphology is attributed to the faster outward diffusion of metal ions through the oxide layer in the oxidation processes. Further changes in morphology during the annealing of hollow Cu, Ni and Fe oxides at higher temperatures in air were examined.

Abstract: . In intermetallic compounds, random vacancy motion is not possible as it would disrupt the equilibrium ordered arrangement of atoms on lattice sites. In view of this limitation, various atomistic models have been proposed, which allow atom-vacancy exchanges to take place without concomitant long range disordering. For a L12 -type A3B structure, the major element A diffuses faster than the minor element B. The trend is attributed to the different diffusing paths; A atoms can diffuse through site exchanges with a neighbouring vacancy on its own sublattice, while the jump of a B atom to a neighbouring site always creates wrong bonds. For L10-type structures such as γ-TiAl, significant diffusion anisotropy is observed; Ti atoms diffuse on the Ti sublattice, while Al atoms also diffuse on the Ti sublattice. The formation of hollow metal oxide nanoparticles through the oxidation process has been studied by transmission electron microscopy for Cu, Zn, Al, Pb and Ni. The hollow structure is obtained as a result of vacancy aggregation, resulting from the rapid outward diffusion of metal ions through the oxide layer during the oxidation process. This suggests the occurrence of two different diffusion processes in the formation of hollow oxides.

Abstract: The structural stability of hollow Cu2O and NiO nanoparticles, which were obtained via oxidation of Cu and Ni nanoparticles in air, was studied by transmission electron microscopy (TEM). Hollow Cu2O and NiO were observed to have shrunk at 473 and 623 K in annealing under 5.0×10-5 Pa, respectively, where the reduction reactions from oxides to metals started. As a result of shrinking associated with reduction, hollow oxides turned into solid metal nanoparticles after annealing at higher temperatures for a long time. In addition, hollow oxides shrunk and collapsed through high-temperature oxidation. It was found that shrinking of hollow oxides during oxidation occurs at temperature where the diffusion coefficients of slower diffusing species reach around 10-22 m2s-1. It seems that the hollow oxide nanoparticles tend to shrink and collapse at high temperatures because the hollow structures are energetically unstable.

Abstract: The formation of hollow metal oxide nanoparticles through oxidation process has been studied by transmission electron microscopy for Cu, Zn, Al, Pb and Ni in order to clarify the detailed formation mechanism of hollow oxide nanoparticles and their governing factors. For Cu, Zn, Al and Ni nanoparticles, hollow oxide nanoparticles are obtained as a result of vacancy aggregation in the oxidation processes. These results arise from faster outward diffusion of metal ions through the oxide layer in the oxidation processes. On the other hand, Pb nanoparticles turn to solid PbO, because the diffusivity difference DPb < DO in PbO leads to no formation of vacancy clusters.

Abstract: The formation of hollow zinc oxide has been studied by oxidation and subsequent thermal treatment of nanometer-sized zinc particles using in-situ TEM. The zinc particles produced under UHV condition were exposed to air at room temperature for 0.6 ks, which resulted in the formation of oxide layer with thickness of 3 nm. Subsequent heating inside UHV chamber of TEM induced the evaporation of the inner zinc, which resulted in the formation of hollow zinc oxide. The produced hollow zinc oxide had the wurtzite structure. Based upon the vapor pressure of the inner zinc, it seems reasonable to consider that the internal zinc vapor leaks away through the interface between the oxide layer and the amorphous carbon film used as a supporting substrate.

Abstract: Oxidation behavior of Cu nanoparticles in the formation process of hollow Cu2O spheres was investigated by TEM. The thickness of Cu2O layers on Cu nanoparticles oxidized at 323 K in air was measured as a function of oxidation time. At the initial stage of oxidation until the oxide film with 2.5 nm in thickness is formed, the thickness of oxide films on Cu nanoparticles with the diameter of 10, 20 and 35 nm shows a nearly equal value regardless of diameter of Cu. After the formation of 2.5 nm layer, however, the growth rate of the oxide films on smaller nanoparticles becomes slower than that on larger nanoparticles. This result suggests that the voids formed at the Cu/Cu2O interface prevent Cu atoms from diffusing outward across the interface because the volume ratio of voids to inner Cu in smaller nanoparticles is much larger than that in larger nanoparticles.