Zwitterionic porphyrin (tetrakis {4-(2-carboxyethyl)pyridinio}porphyrin (TPyCP)) with four pyridinium and carboxyl groups in the molecule was synthesized. The adsorption behaviour of TPyCP on the montmorillonite clay surface was examined in an aqueous colloidal solution. While the adsorption maximum λmax of TPyCP was 424 nm in water, it shifted to longer wavelengths on complex formation with clay. The λmax on the exfoliated clay surface was 450 nm, and that in the stacked clay sheets was 471 nm, respectively. Under alkaline conditions ([NaOH] = 2 × 10–4 M), the stacking behaviour of the clay was completely suppressed. It emerged that anionic parts in the porphyrin molecule can suppress the stacking of clay sheets. Judging from the quantitative analysis, the maximum adsorption amount of TPyCP was 100% vs. cation exchange capacity (CEC) of the clay. As the adsorption density of TPyCP increased, λmax shifted slightly to longer wavelengths due to the interactions between adjacent porphyrins. When the loading level of TPyCP was 200% vs. CEC, the stacking of TPyCP was indicated. The average stacking layer number was calculated to be 1.48. On the other hand, it is known that tetra cationic porphyrins without anionic parts do not form such stacking structures. Thus, it seems that zwitterionic porphyrin has the potential to form a three dimensional structure through electrostatic interactions between porphyrins on the clay surface.

Knowledge of the groundwater age is indispensable for understanding groundwater flow in crystalline rocks. The present study is the first to discuss the radiocarbon ages of groundwater in Abukuma granite, Fukushima Prefecture, northeast Japan. The vertical profiles of 14C dates and δ13C are obtained from 3 boreholes (depths of 140, 230, and 306 m). Chemical and carbon isotopic compositions suggest that dead-carbon contamination of groundwater occurred during groundwater storage in the fractures. 14C concentration was corrected by using isotopic mass balance in which dead-carbon contamination of the groundwater was considered. The 14C dates ranged from modern to ≃16 ka. The relationship between tritium and 14C data in 1 borehole suggests the simultaneous inflow of shallow groundwater to deeper levels occur for the depths between 60 and 100 m. The vertical profiles of 14C dates indicate a relatively constant age of 10–16 ka for groundwater deeper than 100 m, which may have been influenced by rapid sea-level changes after the glacial period.

Extended abstract of a paper presented at Microscopy and Microanalysis 2008 in Albuquerque, New Mexico, USA, August 3 – August 7, 2008

The immobilization of U(VI) by C-S-H phases under conditions relevant for the cementitious near field of a repository for radioactive waste has been investigated. C-S-H phases have been synthesized using two different procedures: the “direct reaction” method and the “solution reaction” method.

The stabilities of alkaline solutions of U(VI) (presence of precipitates or colloidal material) were studied prior to sorption and co-precipitation tests in order to determine the experimental U(VI) solubility limits. These U(VI) solubility limits were compared with the U(VI) solubilities obtained from thermodynamic speciation calculations assuming the presence of combinations of different solid U(VI) phases. The solid phase controlling U(VI) solubility in the present experiments was found to be CaUO4(s).

The U(VI) uptake kinetics and sorption isotherms on C-S-H phases with different C:S ratios were determined under various chemical conditions; e.g., sorption and co-precipitation experiments and different pH’s. U(VI) was found to sorb fast and very strongly on C-S-H phases with distribution ratios (Rd values) ranging in value between 103 L kg-1 and 106 L kg-1. Both sorption and co-precipitation experiments resulted in Rd values which were very similar, thus indicating that no additional sorption sites for U(VI) were generated in the co-precipitation process. Furthermore, C-S-H synthesis procedures did not have a significant influence on U(VI) uptake. The U(VI) sorption isotherms were found to be non-linear, and further, increasing Ca concentrations resulted in increasing U(VI) uptake. The latter observation suggests that U(VI) uptake is controlled by a solubility-limiting process, while the former observation further indicates that pure Ca-uranate is not the solubility-limiting phase. It is proposed that a solid solution containing Ca and could control U(VI) uptake by C-S-H phases.

Extended abstract of a paper presented at Microscopy and Microanalysis 2007 in Ft. Lauderdale, Florida, USA, August 5 – August 9, 2007

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2006

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2006

Shiga toxin (Stx)-producing Escherichia coli (STEC) strains isolated from a seagull in Japan were examined. A total of 50 faecal samples was collected on a harbour bank in Hokkaido, Japan, in July 1998. Two different STEC strains, whose serotypes were O136[ratio ]H16 and O153[ratio ]H− , were isolated from the same individual by PCR screening; both of them were confirmed by ELISA and Vero cell cytotoxicity assay to be producing active Stx2 and Stx1, respectively. They harboured large plasmids, but did not carry the haemolysin or eaeA genes of STEC O157[ratio ]H7. Based on their plasmid profiles, antibiotic resistance patterns, pulsed-field gel electrophoresis analysis (PFGE), and the stx genes sequences, the isolates were different. Phylogenic analysis of the deduced Stx amino acid sequences demonstrated that the Stx toxins of seagull-origin STEC were closely associated with those of the human-origin, but not those of other animal-origin STEC. In addition, Stx2Φ-K7 phage purified from O136 STEC resembled Stx2Φ-II from human-origin O157[ratio ]H7, and was able to convert non-toxigenic E. coli to STEC. These results suggest that birds may be one of the important carriers in terms of the distribution of STEC.

β-FeSi2 is a promising material for the application of various electronic, optoelectronic and energy devices. We present here the semiconducting properties of β-FeSi2 films on Si(100) substrate prepared by laser ablation method. Samples were grown using poly-crystalline bulk β-FeSi2 prepared by horizontal gradient freeze method. For the monitoring of growth, in-situ observation of ablation plume was made through fluorescence spectroscopy. Reflection of highenergy electron beam diffraction (RHEED) was also made in-situ to see the surface morphology. Characterization of the films by X-ray diffraction presented purely P3(220) orientation. Raman scattering measurements at room temperature also indicated that the grown films are semiconducting β-FeSi2. Optical absorption spectra at room temperature showed absorption coefficient higher than 105 cm−1 above the band-gap (˜1.2 eV). It was revealed that high quality semiconducting β-FeSi2 films can be fabricated by laser ablation method without post-annealing.

The sorption behavior of europium onto two iron-oxides, goethite and magnetite, focused on the effect of carbonate species concentration was investigated in 0.01 M NaClO4 solution by the batch method over a pH range of 4 to 11. It was found that sorption of europium was enhanced in the higher concentration solution of carbonate species for both materials. The zeta-potential of goethite in the solutions including sodium bicarbonate was also measured to estimate the effect of sorbed carbonate species. Our experimental results and model calculation suggest that the production of surface carboxylic group FeOCOO by the sorption of carbonate species lowered the zeta-potential and enhanced europium sorption.

We report on the synthesis of β-FeSi2 bulk materials using Horizontal Gradient Freeze (HGF) method. Chunk and powder FeSi2 or high-purity Fe (4N) and Si (9N) were used as starting materials. Three values (1:2, 2:5 and 1:3) of the Fe:Si ratio were selected in the very narrow α and β ranges of the equilibrium phase diagram. Samples were melted between 1300°C and 1500°C in high purity graphite crucibles covered with boron nitride. After cooling, the samples were kept at 800°C and 900°C during 66 to 100 hours, leading to transformation from α to β phase. Cooling rate and annealing time were taken as the two main parameters to optimize the growth conditions. Principal structural characterization was made by X-ray diffraction (XRD). Correlation with stoichiometry was achieved using the results of Rutherford Backscattering Spectroscopy (RBS) and Electron Probe X-Ray Micro Analysis (EPXMA). The samples obtained from 1:2 ratio exhibited mainly β phase while the 2:5 ratio specimens revealed almost α phase structure. The samples prepared with 1:3 ratio was found as a mixture of α and β phases under Si-rich conditions.

Furnace annealing (FA) and rapid thermal annealing (RTA) were made for Cd+ ion-implanted GaAs with Cd concentration, [Cd] from 1×1016cm−3 to 3×1021 cm−3. In FA samples, Raman scattering spectra exhibited a single peak at 292 cm−1 for entire [Cd] range which is LO-phonon mode from (100) GaAs. In RTA samples, LO-phonon mode is a single peak for [Cd]<1×1019cm−3 but with growing [Cd], TO-phonon mode appears for [Cd] 1×1020cm3 and becomes a dominant signal for [Cd]=3×1021 cm−3. The quenching of LO-phonon mode with increasing [Cd] was more clearly observed in RTA samples than in FA ones. Hall-effects results, however, showed that activation rate of RTA samples is 6–7 times larger than that of FA ones for [Cd] 1×1021 cm−3. 2K photoluminescence spectra revealed that in FA samples multiple shallow emissions associated with Cd are formed while in RTA ones the dominant emission is the band to Cd acceptor transition.

Sorption behaviors of neptunium (V) on naturally-occurring magnetite (Fe3O4) and goethite (α-FeOOH) in 0.1M NaN03 electrolyte solution under aerobic conditions were interpreted using the surface complexation model (SCM). The surface properties of these materials were experimentally investigated by C02-free potentiometric titration, and SCM parameters for the constant capacitance model, such as protonation/deprotonation constants of the surface hydroxyl group, were determined. The number of negatively charged sorption sites of goethite rapidly increased with the increase of the bulk solution pH compared with that of magnetite and this tendency was similar to the pH dependence of neptunium sorption. This implies that the neptunyl cation, NpO2+, plays a dominant role in possible sorption reactions. Assuming that the dominant surface complex is XO-NpO2, modeling by means of SCM was carried out, and the results were found to agree with experimental data.

Diffusion experiments of radionuclides in compacted sodium bentonite with a dry density of 1.0 g/cm3 were performed in nitrogen gas atmosphere at 90 °C for 208 d and 375 d. The corrosion experiments of crushed radioactive glass, JSS-A, carried out simultaneously to provide the source of the radionuclides for the diffusion experiments. The normalized elemental mass losses of cesium isotopes and 238Pu were lower than those of boron (ca. 10 g/m2) probably because of the difference of sorption and/or precipitation. The apparent diffusion coefficients of 238Pu, 234U and 125Sb were determined to be 2x 10-14 m2/s, 5x 10-12 m2/s and 2x 10-12 m2/s, respectively. The distribution coefficient of Pu estimated from the diffusion data was of the same order as that from batch sorption experiments. The glass corrosion and the plutonium diffusion were described by the geochemical codes PHREEQE, STRAG4 and GESPER. The calculation results well fitted the observed data.

All-oxide S-N-S (superconductor-normal layer-superconductor) junctions having a planar structure are fabricated and their electrical characteristics in the normal state are investigated. The superconducting electrodes are composed of HoBa2Cu3O7−x, and the normal layer is La1.5Ba1.5Cu3O7-y. Conductance characteristics are measured and their behaviors are explained by the geometrical resonance of quasiparticles. A pair potential distribution in the normal layer is estimated from the resonance structure.

Beryllium (Be) depth profiles, carrier profiles, ideality factors (deviation from thermionic emission and diffusion theory) and Schottky barrier heights of Al/p+-GaAs Schottky diodes were investigated by using focused ion beam (FIB) and de-focused ion beam (DFIB) of 40keV Be+, with dose range from 5.0×1012ions/cm2 to 3.4×1014ions/cm2. Differences of the depth profiles between FIB implantation and DFIB implantation were observed, and it was confirmed that depth profiles of the ion implantations were affected by current densities of the ion probes. The other side, it was recognized that the ideality factors and the Schottky barrier heights of the Schottky diodes were depended on effect of thermionic field emission.

Silicidation of titanium on silicon is carried out with the halogen lamp annealing. It is found that the lamp annealing is quite effective in forming an oxide-free and homogeneous titanium disilicide layer with resistivity of 15–17 μohm·cm. Rutherford backscatterring and X-ray diffraction studies show that the halogen lamp annealing over 650 °C for only 60 sec results in disilicide. By a silicidation reaction, arsenic and boron atoms at silicon beneath a titanium layer are incorporated into a formed silicide layer. Arsenic atoms initially in a titanium layer are swept toward the surface as silicidation reaction proceeds. Arsenic atoms in titanium have an effect to retard silicidation reaction.