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PtCu nanoparticles were synthesized with different pH and support conditions
using radiochemical process. The nanoparticle structures were characterized by
transmission electron microscopy, inductively coupled plasma atomic emission
spectrometry, X-ray absorption spectroscopy, and X-ray diffraction techniques.
The nanoparticle structure was relevant to the pH of the precursor solutions.
The lattice parameter of PtCu alloy increased in high pH samples, which
indicates the critical effect of metal ion adsorption in precursor solution on
Antiviral activity of metallic Ag nanoparticles immobilized on textile fabrics
were investigated. The Ag nanoparticles synthesized by radiochemical process are
firmly immobilized on the surface of support textile fabrics of cotton. Small Ag
particles of about 2–4 nm were observed together with relatively
large particles of more than 10 nm. The Ag nanoparticles showed antiviral
activity against Influenza A and Feline Calicivirus. The antiviral activity
significantly depended on the concentration of the Eagle’s minimal
essential medium. It was implied that the surface passivation by inhibitory
agent lead to the deactivation of metallic Ag nanoparticles.
Electrode catalysts composed of carbon supported PtRu nanoparticles (PtRu/C) synthesized by radiochemical process were annealed to control the PtRu substructure to enhance catalytic activity. The substructure of the PtRu nanoparticles synthesized by using high-energy electron beam under acidic condition was Pt-rich core/Ru-rich shell type, reflecting the redox potentials of each precursor ions. The material characterization techniques revealed that the reductive annealing led to the mixing of PtRu both in the core and on the surface. The sample with annealing temperature of 300°C for 5 hour showed the highest methanol oxidation current, 2.3 times higher than that obtained with before annealing.
Carbon supported Pt-SnO2 electrocatalysts with different Sn/Pt molar ratios were prepared by an electron beam irradiation method. Dissolved gas conditions in the vials irradiated with electron beam were controlled to air or Ar. The results of the material analyses showed that both Pt and SnO2 were immobilized onto carbon support in all catalysts. Bubbling Ar to the precursor solution led to steady change of metal contents in response to the precursor concentrations. The ethanol oxidation activity plotted against Sn/Pt ratio behaved differently with dissolved gas condition of the vial. This difference is discussed with supposed existing state of SnO2 in connection with the reduction process of Pt and Sn.
HoxEr1-xN (x=0.25, 0.5, 0.75) samples were synthesized by nitriding of HoxEr1-x alloy bars and their thermal conductivity κ were measured. The measured κ values were comparable to those of stainless steel and Er3Ni. Ho0.5Er0.5N showed the highest κ of the present three samples. The thermal diffusivity calculated from the κ and the specific heat indicates that Ho0.5Er0.5N is a very promising regenerator material for the cryocoolers. The electrical resistivity ρ was also measured as a function of temperature.
A nanoparticle catalyst of PtRuAu/C was synthesized by including an Au precursor in the radiolytic process for preparing a PtRu/C catalyst. Their methanol oxidation activity and electrochemical durability were measured by linear sweep voltammetry before and after potential cycling treatment. PtRuAu/C had a significantly higher durability than PtRu/C while maintaining a comparable high activity. The morphology and substructure of the nanoparticles were investigated by energy-dispersive x-ray spectroscopy, x-ray diffraction, and x-ray absorption fine structure spectroscopy. Metallic nanoparticles with diameters of about 2 nm were obtained; they probably had Pt-core/PtRu-shell structures. Transmission electron microscopy observations after potential cycling revealed that 2-nm-diameter nanoparticles containing Au did not coarsen, whereas nanoparticles without Au coarsened significantly to 3.7 nm. Some crystal defaults were observed in the coarsened particles, implying that the coarsening was caused by Ostwald ripening. The Au addition to catalyst particles consisting of PtRu inhibits coarsening and consequently improves the electrochemical durability.
Cryopreservation using an aluminium cryo-plate was successfully applied to in vitro-grown strawberry (Fragaria × ananassa Duch.) shoot tips. The shoots were cold-hardened at 5°C for 3 weeks with an 8-h photoperiod. The shoot tips (1.5–2.0 mm × 0.5–1.0 mm) were dissected from the shoot and pre-cultured at 5°C for 2 d on Murashige and Skoog medium containing 2 M glycerol and 0.3 M sucrose. The pre-cultured shoot tips were placed on the aluminium cryo-plate containing ten wells embedded in alginate gel. Osmoprotection was performed by immersing the cryo-plates in a loading solution (2 M glycerol and 0.8 M sucrose) for 30 min at 25°C. Dehydration was performed by immersing the cryo-plates in plant vitrification solution 2 for 50 min at 25°C. Then, the cryo-plate with shoot tips was transferred into an uncapped cryotube that was held on a cryo-cane and directly immersed into liquid nitrogen (LN). After storage in LN, shoot tips attached to the cryo-plate were directly immersed into 2 ml of a 1 M sucrose solution for regeneration. Using this procedure, the average regrowth level of vitrified shoot tips of 15 strawberry cultivars reached 81%. This new method has many advantages and will facilitate the cryostorage of strawberry germplasm.
Low-voltage-driven organic thin-film transistors (organic TFTs) with spatially controlled threshold voltages (−1.2 and −0.36 V) were fabricated for the first time. Using the microcontact printing method, tetradecylphosphonic acid (HC14-PA) and pentadecylfluoro-octadecylphosphonic acid (FC18-PA) were transferred to form ultrathin layers in different regions on a substrate. Together with plasma-grown aluminum oxide (AlOx) layer, the stamped layers were shown to have equal insulating ability as the dipped method monolayer. The feasibility of the area-selective stamping method was displayed using locally controlled inverter circuits. The shift of turn-on voltage for those transistors was consistent with the threshold voltage shift of the transistors.
We have successfully achieved a transconductance of 0.76 S/m for organic thin-film transistors with 4 V operation, which is the largest value reported for organic transistors fabricated using printing methods. Using a subfemtoliter inkjet, silver electrodes with a line width of 1 µm and a channel length of 1 µm were printed directly onto an air-stable, high-mobility organic semiconductor that was deposited on a single-molecule self-assembled monolayer-based gate dielectric. On reducing the droplet volume (0.5 fl) ejected from the inkjet nozzle, which reduces sintering temperatures down to 90 °C, the inkjet printing of silver electrodes was accomplished without damage to the organic semiconductor.
Nanoparticle catalyst of PtRuAu/C for direct methanol fuel cell anodes was synthesized by a radiolytic process. Its methanol oxidation activity and the electrochemical durability were evaluated by using the linear sweep voltammetry and the cyclic voltammety. The Au addition significantly improved the durability in comparison with PtRu/C catalyst without losing its high activity. The atomic structure was characterized with techniques of the transmission electron microscopy, the X-ray diffraction, the X-ray fluorescence spectroscopy and the X-ray absorption fine structure. These results implied that the arrangement of Pt and Ru atoms in the PtRuAu/C has no significant difference from that without Au, possessing a structure of Pt rich core and PtRu alloy shell. We concluded that the improvement in durability could originate from these PtRu nanoparticles decorated with Au, but not from particles with high Au contents.
A magnetic refrigeration test was performed using a test device filled with spherical GdN material synthesized by the hot isostatic pressing (HIP) method. Refrigeration with an active magnetic regenerator cycle was tested in the temperature range between 48 and 66 K, with the field changing from 1.2 to 3.7 T and 2.0 to 4.0 T at upper and lower sides of the regenerator bed filled with the GdN spheres, respectively. Temperature spans about of 2 K were obtained at both sides, and the total temperature span in each cycle attained about 5 K. The specific heat of the material was measured to calculate the magnetic entropy change ΔS and the adiabatic temperature change ΔT induced by the magnetic field change ΔH. It was suggested that for a given ΔH, larger ΔS and ΔT can be exploited when demagnetized to lower H, especially, to zero field.
Catalysts in which Pt and Cu are immobilized on support particles of γ-Fe2O3 were synthesized by the radiolytic process and were evaluated for CO oxidation in a gas flow mixture (1% CO, 0.5% O2, 67.2% H2 and N2 balance) by measuring the CO concentration in the outlet gas. The Pt/Cu atomic ratios of the as-synthesized catalysts were determined to be 100:0, 90:10, 78:22, 50:50, 21:79, and 11:89, and the total metal loadings determined by chemical analyses were 10 wt%. Material characterization was performed using X-ray diffraction, X-ray absorption near edge structure, and transmission electron microscopy, and it was indicated that the composite catalysts consist of Pt-Cu bimetallic grains immobilized on the support at higher Pt-loading, while CuO with poor crystallinity is also observed at lower Pt-loading. The catalytic activity decreased as the Pt-loading was decreased to 50 at%, and also with increasing temperature. However, as the Pt-loading was further decreased, the activity contrariwise increased, and increased with increasing temperature up to 100 °C. The sample containing only 11 at% Pt exhibited the highest activity at 100 °C, which is higher than that of the commercial catalyst measured for comparison, and given at a lower temperature than that for the commercial catalyst. This enhanced activity, despite the low Pt-loading, could be attributed to oxygen supply via CuO from the O2-poor atmosphere to PtCu bimetallic grains trapping CO molecules. This new material is promising for use as a catalyst to purify hydrogen gas fed to a polymer electrolyte fuel cell.
Instability waves in a laminar planar jet are extracted using hybrid unsteady-flow simulation combining particle tracking velocimetry (PTV) and direct numerical simulation (DNS). Unsteady velocity fields on a laser sheet in a water tunnel are measured with time-resolved PTV; subsequently, PTV velocity fields are rectified in a least squares sense so that the equation of continuity is satisfied, and they are transplanted to a two-dimensional incompressible Navier–Stokes solver by setting a multiple of the computational time step equal to the frame rate of the PTV system. As a result, the unsteady hybrid velocity field approaches that of the measured one over time, and we can simultaneously acquire the unsteady pressure field. The resultant set of flow quantities satisfies the governing equations, and their resolution is comparable to that of numerical simulation with the noise level much lower than the original PTV data. From hybrid unsteady velocity fields, we extract eigenfunctions using bi-orthogonal decomposition as a spatial problem for viscous instability. We also investigate stability/convergence characteristics of the hybrid simulation referring to linear stability analysis.
Bimetallic nanoparticles of PtCu and PtNi supported on iron oxide particles were synthesized by a new method employing a 4.8-MeV electron beam as a trigger for reduction of their aqueous ions, and their CO oxidation catalysis was evaluated to find activities enhanced by the alloying. Sample materials of PtCu (PtNi) bimetallic grains supported on γ-Fe2O3 particles were synthesized by irradiating with the electron beam a glass vial containing precursors in an aqueous solution. The vial contains aqueous ions of platinum and copper (nickel) and γ-Fe2O3 particles of average size of 30 nm. The irradiation induces water radiolysis generating reducing species, such as hydrated electrons, and metallic nanograins are formed and stabilized on the support material. The irradiation was finished in several seconds without using any organic solvent and any surfactant. The average grain sizes observed with a TEM were around 3 nm in diameter. XRD patterns of PtCu samples exhibited the FCC structure with peak shifts obeying the Vegard’s law at low Cu concentrations. X-ray absorption spectra measured at edges of the constituent elements indicated that Pt is in the metallic state and coordinates certainly with Cu or Ni. Catalytic activity of CO oxidation of the material was evaluated by measuring residual CO contents in air in contact with the sample material by using a gas-chromatograph. The activities of the PtCu and PtNi samples were higher than that of monolithic Pt on γ-Fe2O3. The correlation between the atomic structure in these nanograins and their activities was investigated, which indicated that the random alloy enhances the activity. These bimetallic nanoparticles are expected as catalysts for preferential oxidation of CO in hydrogen gas fed to fuel cells.
Composite nanoparticles consisting of gold and iron-oxide were radiochemically synthesized in aqueous solution systems by using polyethylene glycols. The gold particles with average diameter of 3 nm were firmly immobilized on the surface of the support iron-oxide nanoparticles. The composite nanoparticles specifically adsorbed sulfur-containing amino acids by a Au-S bonding.
We synthesized HoxEr1−xN (x =0.1, 0.3, 0.5, 0.7, 0.9) by the carbothermic reduction method. The magnetic entropy change, ΔS, which is an indicator of performance of magnetocaloric effect, MCE, was obtained from data sets of magnetization M (H, T) measured at various temperature, T, and magnetic field, H, through the Maxwell equations. The Thus obtained ΔS vs. T curves have peaks at temperatures depending on x in a range of 8–18 K. ΔS values of HoxEr1−xN expressed in terms of J K−1 m−3 were higher than those of intermetallic compounds of rare earth and transition metals previously reported. These ΔS peak plots are along a convex curve, which may indicate an interaction between the two components.
PtRu bimetallic nanoparticles supported on carbon nanoparticle (PtRu/C) catalysts were synthesized with radiation irradiation. The samples were structural analyzed by techniques of X-ray absorption fine structure (XAFS), transmission electron microscope (TEM) and X-ray diffraction (XRD). The results indicated that PtRu/C catalysts which prepared by an electron beam irradiation had more homogeneous atomic arrangement than that prepared by a gamma-ray irradiation. We found a clear correlation between the atomic structure and the catalytic activity of PtRu/C catalysts. These results supported the bi-functional mechanism.
Nano-sized PtRu catalysts supported on carbon nanoparticles were synthesized by a polyol process. The PtRu catalyst prepared at pH=3 indicated higher catalysis for methanol oxidation than one prepared at pH=5.5. The samples were analyzed by techniques of the extended X-ray absorption fine structure (EXAFS), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF). Their results showed that the pH of the precursor solution during the polyol process affected the substructure of the PtRu nanoparticles. The correlation of the substructure with the catalytic activity was studied.
Amounts of oligonucleotides adsorbed onto the Au/γ-Fe2O3 composite nanoparticles synthesized by gamma-ray irradiation and picked up by a magnet were evaluated using fluorescence technique. The adsorbing capacity of the oligonucleotides on our nanoparticles are larger than a commercial magnetic beads for a separation of biomolecules.
Z-type hexagonal ferrite samples in which cobalt is partially substituted with iron, Ba3Co2-xFe24+xO41 (x = 0, 0.2, 0.4, 0.6), were prepared by the ceramic process under a sintering oxygen partial pressure, PO2 = 21.3 or 101.3 kPa, at 1573 K. The influence of the substitution ratio and oxygen partial pressure on the complex permeability was investigated by examining the cobalt distribution over various cation sites in the Z-type structure with the neutron powder diffraction analysis performed at 294 K (neutron wave length was 1.006Å). The neutron diffraction pattern was studied with the Rietveld method. A significant difference in the preferential occupation of cobalt on various kind of cation sites was observed between the samples obtained under PO2 = 21.3 and 101.3 kPa. Almost all cobalt atoms are on the 12k octahedral site at the boundary between S- and R-blocks in the sample of x = 0, PO2 = 21.3 kPa. On the other hand, in the sample of x = 0, PO2 = 101.3 kPa, cobalt atoms are as well on other sites, the 12k octahedral site at the boundary between S- and T-blocks, the 4e tetrahedral site in S-block, the 2a octahedral site in T-block and the 2d five fold (trigonal bypiramid) site in T-block.