Synthesis, crystal structure, local structure, and magnetic properties of polycrystalline and single-crystalline CePtAl

Ota, Kyugo*; Watabe, Yuki*; Haga, Yoshinori; Iesari, F.*; Okajima, Toshihiko*; Matsumoto, Yuji*

Symmetry (Internet), 15(8), p.1488_1 - 1488_13, 2023/07

https://doi.org/10.3390/sym15081488

Study on the relation between the crystal structure and thermal stability of FeUO and CrUO

Akiyama, Daisuke*; Kusaka, Ryoji; Kumagai, Yuta; Nakada, Masami; Watanabe, Masayuki; Okamoto, Yoshihiro; Nagai, Takayuki; Sato, Nobuaki*; Kirishima, Akira*

Journal of Nuclear Materials, 568, p.153847_1 - 153847_10, 2022/09

https://doi.org/10.1016/j.jnucmat.2022.153847

FeUO, CrUO, and FeCrUO are monouranates containing pentavalent U. Even though these compounds have similar crystal structures, their formation conditions and thermal stability are significantly different. To determine the factors causing the difference in thermal stability between FeUO and CrUO, their crystal structures were evaluated in detail. A Raman band was observed at 700 cm in all the samples. This Raman band was derived from the stretching vibration of the O-U-O axis band, indicating that FeCrUO was composed of a uranyl-like structure in its lattice regardless of its "x"' value. Mssbauer measurements indicated that the Fe in FeUO and FeCrUO were trivalent. Furthermore, FeCrUO lost its symmetry around Fe with increasing electron densities around Fe, as the abundance of Cr increased. These results suggested no significant structural differences between FeUO and CrUO. Thermogravimetric measurements for UO, FeUO, and CrUO showed that the temperature at which FeUO decomposed under an oxidizing condition (approximately 800 C) was significantly lower than the temperature at which the decomposition of CrUO started (approximately 1250 C). Based on these results, we concluded that the decomposition of FeUO was triggered by an "in-crystal" redox reaction, i.e., Fe U Fe U, which would not occur in the CrUO lattice because Cr could never be reduced under the investigated condition. Finally, the existence of Cr in FexCrUO effectively suppressed the decomposition of the FeCrUO crystal, even at a very low Cr content.

Experimental determination of the photooxidation of aqueous I as a source of atmospheric I

Watanabe, Kosuke*; Matsuda, Shohei; Cuevas, C. A.*; Saiz-Lopez, A.*; Yabushita, Akihiro*; Nakano, Yukio*

ACS Earth and Space Chemistry (Internet), 3(4), p.669 - 679, 2019/04

https://doi.org/10.1021/acsearthspacechem.9b00007

The photooxidation of aqueous iodide ions (I) at sea surface results in the emission of gaseous iodine molecules (I) into the atmosphere. It plays a certain role in the transport of iodine from ocean to the atmosphere in the natural cycle of iodine. In this study, we determined the photooxidation parameters, the molar absorption coefficient (()) and the photooxidative quantum yields (()) of I, in the range of 290-500 nm. Through the investigation of the influence of pH and dissolved oxygen (DO) on (), the subsequent emission rates of I following the photooxidation of I in deionized water solution (pH 5.6, DO 7.8 mg L) and artificial seawater solution (pH 8.0, DO 7.0 mg L) were estimated. A global chemistry-climate model employed herein to assess the I ocean emission on a global scale indicated that the photooxidation of I by solar light can enhance the atmospheric iodine budget by up to 8% over some oceanic regions.

Evaluation of effective dose coefficient with variation of absorption fraction in gastrointestinal system for ingestion of radiocesium

Pratama, M. A.; Takahara, Shogo; Hato, Shinji*

Hoken Butsuri, 52(3), p.200 - 209, 2017/09

https://doi.org/10.5453/jhps.52.200

The purpose of this study is to identify the significance of the change in the intestinal absorption rate values the ( value) to the change of dose coefficient as well as to provide a list of dose coefficients which each of the value corresponds to a specific intestinal absorption rate and age groups. In the range of 0-1, 10 different values of for 1 year, 5 years old, and adult group were chosen and used in a separate calculation by using, a biokinetic compartment model, DCAL. It was found that the lower values of intestinal absorption rate lead to a significant decrease of the committed effective coefficient for adult. Oppositely for children, the decrease of committed effective coefficient was not as significant. This study also suggests that the significance of dose coefficient change due to the variation of substantially depends on the biological half-life of the radionuclide and the mass of organs and tissues in human body.

Hydrogen absorption behavior on zirconium under -radiolysis of nitric acid solution

Ishijima, Yasuhiro; Ueno, Fumiyoshi; Abe, Hitoshi

Nihon Genshiryoku Gakkai Wabun Rombunshi, 16(2), p.100 - 106, 2017/05

https://doi.org/10.3327/taesj.J16.018

Zirconium (Zr) has been used as a structural material at the spent nuclear fuel reprocessing plant in Japan because of its excellent corrosion resistance against nitric acid solution. And the radiolytic hydrogen is known to be generated in the spent nuclear fuel solution. Zr is known to be highly susceptible to hydrogen embrittlement. Therefore, evaluating the radiolytic hydrogen absorption behavior of Zr in nitric acid solution (HNO) is essential. In this study, immersion tests were conducted on Zr in nitric acid solutions under -ray irradiation to evaluate its radiolytic hydrogen absorption behavior. Results showed that hydrogen concentration on Zr increased both in 1-3 mol/L HNO and pure water at 5 and 7 kGy/h after immersion. The amount of hydrogen absorption on Zr under -ray irradiation had a direct correlation with the radiolytic hydrogen generation value in HNO. The results of glow discharge optical emission spectrometry, thermal desorption spectroscopy, and X-ray diffraction result shows that the absorbed radiolytic hydrogen generated a hydride on the surface of Zr.

Chemical states of trace-level strontium adsorbed on layered oxide by XPS and XANES under total reflection condition

Baba, Yuji; Shimoyama, Iwao

Photon Factory Activity Report 2016, 2 Pages, 2017/00

http://pfwww.kek.jp/acr/2016pdf/u_reports/pf16b0047.pdf

In order to elucidate the adsorption states of radioactive Sr-90 in soil, chemical bonding states of non-radioactive strontium adsorbed on layered oxide (mica) have been investigated by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) spectroscopy. Since the number of atoms in radioactive Sr-90 is extremely small, the XPS and XANES were measured under total reflection condition of the incident X-rays. The detection limit in total reflection XPS was about 150 pg/cm, which corresponds to 300 Bq of Sr-90. The Sr 2p core-level energy in XPS shifted to lower energy with the decrease in the thickness of Sr layer. Also, the Sr 2p Sr 4d resonance energy in XANES shifts to lower energy with the decrease in the thickness. On the basis of a simple point charge model, it was elucidated that the chemical bond between Sr and mica surface becomes ionic with the decrease in the adsorbed amount of strontium.

Infrared absorption and Raman scattering spectra of water under pressure via first principles molecular dynamics

Ikeda, Takashi

Journal of Chemical Physics, 141(4), p.044501_1 - 044501_8, 2014/07

https://doi.org/10.1063/1.4890369

From both the polarized and depolarized Raman scattering spectra of supercritical water a peak located at around 1600 cm, attributed normally to bending mode of water molecules, was experimentally observed to vanish, whereas the corresponding peak remains clearly visible in the measured infrared (IR) absorption spectrum. In this computational study a theoretical formulation for analyzing the IR and Raman spectra is developed via first principles molecular dynamics combined with the modern polarization theory. We demonstrate that the experimentally observed peculiar behavior of the IR and Raman spectra for water are well reproduced in our computational scheme. We discuss the origins of a feature observed at 1600 cm in Raman spectra of ambient water.

Characterization of F-irradiated graphite surfaces using photon-stimulated desorption spectroscopy

Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Nath, K. G.

Surface and Interface Analysis, 38(4), p.352 - 356, 2006/04

https://doi.org/10.1002/sia.2172

We investigated the orientation nature at the top-most layers of F-irradiated graphite using polarization dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy which incorporates partial electron yield (PEY) detection and photon-stimulated ion desorption (PSID) techniques. The fluorine K-edge NEXAFS spectra conducted in PEY mode show no significant dependence on polarization angles. In contrast, NEXAFS spectra recorded in F ion yield mode show enhanced yields at a feature of 689.4 eV assigned as a *(C-F) state relevant to =C-F sites, which depend on polarization angles. The C-F bonds prefer relatively tilting down the surface at the top-most layer, while the C-F bonds are randomly directed at deeper regions. We conclude that the difference in the orientation structures between the top surface and bulk is reflected in the NEXAFS recorded in the two different detection modes. It was also found that H- and F- PSID NEXAFS spectra are helpful in understanding desorption mechanism, thus in analysing NEXAFS data.

Mechanism of state-specific enhancement in photon-stimulated desorption as studied using a polarization-dependent technique

Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Wu, G.*; Kitajima, Yoshinori*

Surface Science, 593(1-3), p.310 - 317, 2005/11

https://doi.org/10.1016/j.susc.2005.06.076

Using a newly developed rotatable time-of-flight mass spectrometer(R-TOF-MS) and polarized synchrotron radiation, orientation effect on fragmentation and desorption pathways occurring at the top-most layers of molecular solids have been investigated. Reported will be polarization-angle dependencies of TOF mass spectra, high-resolution electron- and ion-NEXAFS in condensed chlorobenzene.

Embrittlement and fracture behavior of pre-hydrided cladding under LOCA conditions

Nagase, Fumihisa; Fuketa, Toyoshi

Proceedings of 2005 Water Reactor Fuel Performance Meeting (CD-ROM), p.668 - 677, 2005/10

A systematic research program on high burnup fuel behavior under LOCA conditions is being conducted at JAERI. As a part of the program, integral thermal shock tests simulating the whole LOCA sequence were conducted with Zircaloy-4 fuel claddings, irradiated to 39 and 44 GWd/t at a PWR, to investigate behavior and condition of cladding fracture during quenching for safety evaluation. Differences were not clearly observed between irradiated and unirradiated claddings at similar hydrogen concentrations in terms of threshold of fracture during quenching, though the threshold is reduced as initial hydrogen concentration increases. Ductility of pre-hydrided, oxidized and quenched claddings was also evaluated by using ring-tensile and ring-compression tests. Embrittlement criteria (zero-ductility limits) from both the tests were lower than the fracture conditions in the integral thermal shock tests. This indicates that loading conditions should be well simulated to evaluate cladding performance under LOCA conditions.