Preliminary study of fabrication technology for transmutation fuels using surrogate alloy

Journal of Radioanalytical and Nuclear Chemistry - A preliminary study on the fabrication of transmutation fuels was carried out using an injection casting technique. Melts of binary U–Zr, a...     

Effect of organic vapors and potential-dependent Raman scattering of 2,6-dimethylphenylisocyanide on platinum nanoaggregates

The surface-enhanced Raman scattering characteristics of 2,6-dimethylphenylisocyanide (2,6-DMPI) on Pt nanoaggregates, in ambient and electrochemical environments and in the presence of organic vapors, were examined and compared with those on Au nanoaggregates. Due to the exclusive adsorption via the isocyanide group, the NC stretching band was very susceptible to the measurement conditions although the ring associated bands showed negligible peak shifts. In ambient conditions, the peak shift of the NC stretching vibration on Pt (29 cm(-1)) was one half of that on Au (61 cm(-1)), suggesting that the electron donation capability of the isocyanide group to Au was greater than that to Pt. In the electrochemical environment, the NC stretching peak varied linearly with slopes of ～42 and ～36 cm(-1) V(-1) on Pt and Au, respectively. On the other hand, the NC stretching bands of 2,6-DMPI on Pt red-shifted by as much as 15 and 41 cm(-1), in the presence of acetone and ammonia, respectively, corresponding to the lowering of the surface potential of Pt nanoaggregates from +0.2 to -0.2 and -0.8 V, respectively. On Au nanoaggregates, however, acetone appeared to increase the surface potential of Au from +0.2 to +0.3 V, although ammonia decreased the surface potential from +0.2 to -0.4 V. Acetone must then act as an electron donor when interacting with Pt while it serves as an electron acceptor when interacting with Au, in agreement with an ab initio quantum mechanical calculation.     

pH effect on surface potential of polyelectrolytes-capped gold nanoparticles probed by surface-enhanced Raman scattering

Nanoparticles are commonly stabilized through the adsorption of acidic/basic polyelectrolytes around the surface of the particle. One example of these nanoparticles is poly(ethylenimine) (PEI)-capped Au nanoparticles. In this work, we have examined by means of surface-enhanced Raman scattering (SERS) of 2,6-dimethylphenylisocyanide (2,6-DMPI) how much the surface potential of Au nanoparticles is affected by the solution pH through the mediation of the protonation and deprotonation of PEI in contact with Au nanoparticles. In fact, the surface-potential-dependent isocyanide (NC) stretching peak of 2,6-DMPI has shifted sharply around pH 8.5, close to the pK(a) value of the primary amine of PEI. When a negatively charged poly(acrylic acid) (PAA) was deposited onto the PEI, the peak shift of the NC stretching band took place around pH 6.5, close to the average pK(a) value of PEI and PAA. When additional PEI was deposited on PAA, the peak shift of the NC stretching band occurred once again around pH 8.5, indicative of the stronger interaction of upper two polyelectrolyte layers. These data clearly illustrate the usefulness of SERS in the elucidation of a delicate interaction of cationic and anionic polyelectrolytes, especially in layer-by-layer deposition.     

Raman scattering of 4-aminobenzenethiol sandwiched between Ag nanoparticle and macroscopically smooth Au substrate: effects of size of Ag nanoparticles and the excitation wavelength

A nanogap formed by a metal nanoparticle and a flat metal substrate is one kind of "hot site" for surface-enhanced Raman scattering (SERS). Accordingly, although no Raman signal is observable when 4-aminobenzenethiol (4-ABT), for instance, is self-assembled on a flat Au substrate, a distinct spectrum is obtained when Ag or Au nanoparticles are adsorbed on the pendent amine groups of 4-ABT. This is definitely due to the electromagnetic coupling between the localized surface plasmon of Ag or Au nanoparticle with the surface plasmon polariton of the planar Au substrate, allowing an intense electric field to be induced in the gap even by visible light. To appreciate the Raman scattering enhancement and also to seek the optimal condition for SERS at the nanogap, we have thoroughly examined the size effect of Ag nanoparticles, along with the excitation wavelength dependence, by assembling 4-ABT between planar Au and a variable-size Ag nanoparticle (from 20- to 80-nm in diameter). Regarding the size dependence, a higher Raman signal was observed when larger Ag nanoparticles were attached onto 4-ABT, irrespective of the excitation wavelength. Regarding the excitation wavelength, the highest Raman signal was measured at 568 nm excitation, slightly larger than that at 632.8 nm excitation. The Raman signal measured at 514.5 and 488 nm excitation was an order of magnitude weaker than that at 568 nm excitation, in agreement with the finite-difference time domain simulation. It is noteworthy that placing an Au nanoparticle on 4-ABT, instead of an Ag nanoparticle, the enhancement at the 568 nm excitation was several tens of times weaker than that at the 632.8 nm excitation, suggesting the importance of the localized surface plasmon resonance of the Ag nanoparticles for an effective coupling with the surface plasmon polariton of the planar Au substrate to induce a very intense electric field at the nanogap.     

Complete 1H and 13C NMR assignments of sesquiterpene glucosides from Ixeris sonchifolia

Four sesquiterpene glucosides were isolated from Ixeris sonchifolia Hance. The structure of a new compound (1) was assigned as 9beta-monohydroxy-2,12-dioxo-guaia-3,11(13)-dien-1alpha,5alpha,6beta,7alpha,9beta,10alphaH-12,6-olide-9-O-beta-D- glucopyranoside (ixerinoside). In addition, unambiguous and complete assignments of (1)H NMR chemical shifts for crepidiaside A (2), ixerin Z (3), and 11,13alpha-dihydroixerin Z (4) are presented. The assignments were achieved by two-dimensional NMR (gCOSY, gHSQC, gHMBC, NOESY) and one-dimensional nuclear Overhauser effect (NOE) experiments.     

Ultrathin carbon support films for high-resolution electron microscopy of nanoparticles.

We introduce a simple preparation method for ultrathin carbon support films that is especially useful for high-resolution electron microscopy (HREM) of nanoparticles. Oxidized iron nanoparticles were used as a test sample in a demonstration of this method. The film qualities are discussed on the basis of electron-energy-loss spectroscopy (EELS) and image analysis techniques such as thickness maps and histograms. We carried out a comparison between the homemade and commercial film qualities. The relative thickness of the homemade support films was 0.6 times less than that of the commercial films, which was calculated from the EELS analysis, whereas the thicknesses of both carbon support films varied within about 3%. The percentage of the observable area was about 67 +/- 7.6% of the support film. This was about twice as large as the commercial film (32 +/- 9.3%). The HREM image of the sample prepared with our support film improved 9% in brightness and 15% in contrast compared with images obtained with the commercial support.     

Preparation of metallic fuel rodlets for irradiation testing in the HANARO research reactor

U–10 wt% Zr fuel rodlets, which will be irradiated in the HANARO research reactor in order to evaluate the irradiation performance of metallic fuel and validate the in-reactor behavior, were prepared through determined fabrication processes. Injection casting technology was applied to produce U–10Zr fuel slugs, and sodium melt and a bonding process were conducted to bond a fuel slug to the fuel cladding. To seal the end plug to the fuel cladding tube, a gas tungsten arc welding technique was adopted. Based on the results of these experiments, sodium-cooled fast reactor fuel rodlets for irradiation testing in the HANARO research reactor have been soundly fabricated.     

Quantitative and isotopic analysis of released and retained krypton and xenon fission gases from irradiated metallic fuels

We quantitatively measured the amounts and isotopic distributions of the released and retained fission gases (Kr and Xe) from two irradiated metallic fuels (U–10Zr and U–10Zr–5Ce) at approximately 2.9 at.% burnup, using a gas chromatography and a quadrupole mass spectrometer. The obtained Xe/Kr ratios indicate that the released and retained fission gases from the irradiated metallic fuels came primarily from the fission of ²³⁵U, instead of that of heavy isotopes such as ²³⁹Pu and ²⁴¹Pu. The calculated (⁸³Kr + ⁸⁴Kr)/⁸⁶Kr and (¹³¹Xe + ¹³²Xe)/¹³⁴Xe ratios suggest that no fuel rods became defective during the irradiation process.