Dissolution behavior of UO, FeUO, and UO-Zr-stainless steel system samples generated in an oxidative atmosphere in the presence of malonic acid

Tonna, Ryutaro*; Sasaki, Takayuki*; Okamoto, Yoshihiro; Kobayashi, Taishi*

Journal of Nuclear Materials, 605, p.155561_1 - 155561_9, 2025/02

https://doi.org/10.1016/j.jnucmat.2024.155561

Investigation of chemical state of uranium included in simulated waste glass

Katsuoka, Nanako; Akiyama, Daisuke*; Kirishima, Akira*; Nagai, Takayuki; Okamoto, Yoshihiro; Sato, Nobuaki*

2023-Nendo "Busshitsu, Debaisu Ryoiki Kyodo Kenkyu Kyoten" Kenkyu Seika, Katsudo Hokokusho (Internet), 1 Pages, 2024/07

no abstracts in English

Dissolution behavior and aging of iron-uranium oxide

Tonna, Ryutaro*; Sasaki, Takayuki*; Okamoto, Yoshihiro; Kobayashi, Taishi*; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*

Journal of Nuclear Materials, 589, p.154862_1 - 154862_10, 2024/02

https://doi.org/10.1016/j.jnucmat.2023.154862

The dissolution behavior of FeUO compounds formed by a high-temperature reaction of UO with iron, a stainless-steel component of reactor structural materials, was investigated under atmospheric conditions. The compounds were prepared in an electric furnace using UO and FeO as starting materials, and their solid states were analyzed using X-ray diffraction, scanning electron microscopy energy dispersive X-ray spectroscopy, and X-ray absorption fine structure spectroscopy. The concentration of nuclides dissolved in water was examined by performing static leaching tests of FeUO compounds for up to three months. A redox reaction was proposed to occur between trivalent Fe and pentavalent U ions in the early stage of FeUO dissolution. It was thermodynamically deduced that the reduced divalent Fe ion was finally oxidized into a trivalent ion in the presence of dissolved oxygen, and iron hydroxide limited the solubility of Fe. Meanwhile, the concentration of hexavalent U (i.e., uranyl ion) was limited owing to the presence of secondary minerals such as metaschoepite and sodium uranate and subsequently decreased, possibly owing to sorption on Fe oxides, for example. The concentrations of multivalent ions of fission products, such as Ru and Ce, also decreased, likely for the reason above. By contrast, the concentration of soluble Cs ions did not decrease. The validity of this interpretation was supported by comparing the results with the dissolution behavior of a reference sample (Fe-free UO).

Structural investigation of borosilicate glasses by using XAFS measurement in soft X-ray region, 3 (Joint research)

Nagai, Takayuki; Okamoto, Yoshihiro; Yamagishi, Hirona*; Shibata, Daisuke*; Kojima, Kazuo*; Hasegawa, Takehiko*; Sato, Seiichi*; Fukaya, Akane*; Hatakeyama, Kiyoshi*

JAEA-Research 2023-004, 45 Pages, 2023/09

JAEA-Research-2023-004.pdf:6.07MB

The local structure of glass-forming elements and waste elements in borosilicate glasses varies with its chemical composition. In this study, simulated waste glass samples were prepared and the chemical state regarding boron (B), silicon (Si) and waste elements of iron (Fe), cesium (Cs) were estimated by using XAFS measurement in soft X-ray region. To understand the chemical stability of simulated waste glasses, XANES spectra of B K-edge, Fe L, L-edge, and Cs M, M-edge were measured on the glass surface exposed to the leachate. As a result, it was found that the glass surface exposed to the leachate was changed and it was difficult to obtain a clear XANES spectrum. From the B K-edge XANES spectra on glass surfaces exposed to the leachate, an increase in three-coordination of B-O (BO) and a decrease in four-coordination of B-O (BO) were observed compared to the glass surfaces before immersion. The XANES spectra of Fe L, L-edge, and Cs M, M-edge show that as the exposure time in the leachate increases, the Cs present on the glass surface dissolves into the leachate. The XANES spectra of Si K-edge were measured on simulated waste glass surfaces before immersion, and it was confirmed that the change in XANES spectra given by NaO concentration had a larger effect than the waste component concentration.

Local structure analysis of DyN-ZrN solid solutions

Yoneda, Yasuhiro; Tsuji, Takuya; Matsumura, Daiju; Okamoto, Yoshihiro; Takaki, Seiya; Takano, Masahide

Physica B; Condensed Matter, 663, p.414960_1 - 414960_9, 2023/08

https://doi.org/10.1016/j.physb.2023.414960

We performed various synchrotron X-ray measurements to extract local and average structures of DyN-ZrN solid solutions. We performed the nanoscale structural analysis by combining X-ray absorption fine structure and high-energy X-ray diffraction. The DyN-ZrN solid solution has a rock-salt type cubic crystal structure, and there are instabilities such as the chemical order of the metal site and the distribution of the bond length of the nitrogen site.

Dry synthesis of brannerite (UTiO) by mechanochemical treatment

Akiyama, Daisuke*; Mishima, Tomoki*; Okamoto, Yoshihiro; Kirishima, Akira*

High Temperature Materials and Processes, 42(1), p.20220268_1 - 20220268_9, 2023/04

https://www.degruyter.com/document/doi/10.1515/htmp-2022-0268/html

A powder mixture of UO and TiO was mechanochemically treated in a planetary ball mill under Ar atmosphere for 1 h using a tungsten carbide vial and balls as the milling medium. Such mechanochemical (MC) treatment reduced the crystallinity of UO and TiO. The mechanochemically treated powder mixture was heated at 973-1573K for 6 h under Ar atmosphere and analyzed by X-ray diffraction analysis, scanning electron microscopy-energy-dispersive X-ray spectroscopy, and X-ray absorption fine structure analysis. UTiO did not form below 1373K without MC treatment and only the starting materials were observed. At 1473 and 1573K, a small amount of UTiO and equal amounts of UTiO and UO were formed, respectively. The mechanochemically treated sample produced nearly pure UTiO containing small amounts of UO impurities when heated above 1173K for 6 h. UTiO was highly crystalline and uniform regardless of the synthesis temperature.

Structural change by phosphorus addition to borosilicate glass containing simulated waste components

Okamoto, Yoshihiro; Shiwaku, Hideaki; Shimamura, Keisuke*; Kobayashi, Hidekazu; Nagai, Takayuki; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*

Journal of Nuclear Materials, 570, p.153962_1 - 153962_13, 2022/11

https://doi.org/10.1016/j.jnucmat.2022.153962

Simulated nuclear waste glass samples containing phosphorus, which increase the solubility of molybdenum, were prepared and analyzed using synchrotron X-ray Absorption Fine Structure (XAFS) analysis for some constituent elements and Raman spectroscopic analysis of their complex structure. Changes in local structure and chemical state due to different phosphorus additions and waste loading rates were systematically studied. Consequently, no crystalline phase due to the molybdate compound was observed even at a maximum waste content of 30 wt% (corresponding to 1.87 mol% MoO). Oxidation proceeded when the waste-loading rate was increased, whereas the reduction proceeded when phosphorus was added. In some cases, the effects of oxidation and reduction were offset. The local structure around specific elements can be classified as follows; Zn that is affected mainly by the waste-loading rate, Ce that is affected by both the waste-loading rate and phosphorus addition, and Zr element that is not affected by either of them. From the comparison between the analytical results of Mo and other elements, it was considered that the added phosphorus exists as a free PO structural unit and may deprive the alkali metal coordinated to the molybdate ion.

Structure and magnetic properties of Fe nanoparticles in amorphous silica implanted with Fe ions and effect of subsequent energetic heavy ion irradiation

Iwase, Akihiro*; Fukuda, Kengo*; Saito, Yuichi*; Okamoto, Yoshihiro; Semboshi, Satoshi*; Amekura, Hiroshi*; Matsui, Toshiyuki*

Journal of Applied Physics, 132(16), p.163902_1 - 163902_10, 2022/10

https://doi.org/10.1063/5.0102438

Amorphous SiO samples were implanted with 380 keV Fe ions at room temperature. After implantation, some of the samples were irradiated with 16 MeV Au ions. magnetic properties were investigated using a SQUID magnetometer, and the morphology of the Fe-implanted SiO samples was examined using transmission electron microscopy and X-ray absorption spectroscopy (EXAFS and XANES), which showed that the size of Fe nanoparticles was increasing The size of Fe nanoparticles increased with increasing Fe implantation amount; some of the Fe nanoparticles consisted of Fe oxides, and the valence and structure of Fe atoms became closer to that of metallic -Fe with increasing Fe injection amount. The magnetization-field curve of the sample implanted with a small amount of Fe was reproduced by Langevin's equation, suggesting that the Fe nanoparticles behave in a superparamagnetic manner. In addition, when a large amount of Fe was implanted, the magnetization-magnetic field curve shows a ferromagnetic state. These magnetic property results are consistent with the X-ray absorption results. Subsequent 16 MeV Au irradiation crushed the Fe nanoparticles, resulting in a decrease in magnetization.

Deep groundwater physicochemical components affecting actinide migration

Kirishima, Akira*; Terasaki, Mariko*; Miyakawa, Kazuya; Okamoto, Yoshihiro; Akiyama, Daisuke*

Chemosphere, 289, p.133181_1 - 133181_12, 2022/04

https://doi.org/10.1016/j.chemosphere.2021.133181

no abstracts in English

Structural investigation of borosilicate glasses by using XAFS measurement in Soft X-ray region (Joint research)

Nagai, Takayuki; Okamoto, Yoshihiro; Yamagishi, Hirona*; Ota, Toshiaki*; Kojima, Kazuo*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*

JAEA-Research 2021-010, 62 Pages, 2022/01

JAEA-Research-2021-010.pdf:6.05MB

The local structure of glass-forming elements and waste elements in borosilicate glasses varies with its chemical composition. In this study, borosilicate glass frit and simulated waste glass samples were prepared and the local structure and chemical state regarding boron(B), oxygen(O), silicon(Si) and waste elements of iron(Fe), cesium(Cs) were estimated by using XAFS measurement in soft X-ray region. Following results were obtained by XAFS measurements of prepared glass frit and simulated waste glass samples: (1) The effect of NaO concentration on B-O coordination structure is greater than that of the waste elements concentration. (2) The height of pre-edge by O K-edge spectrum depends on the concentration of first transition elements such as Fe in glass samples. Following results were obtained by XAFS measurements of simulated waste glass samples after immersion test to investigate the long chemical stability. (1) A new compound was formed on the sample surface after the immersion test, and changes in the surface state were confirmed by Raman spectroscopy. (2) Cs on the sample surface after immersion test dissolves into the leaching solution. The Si K-edge XANES spectra of borosilicate glass frits and simulated waste glass samples included lanthanides oxide were measured, and following was confirmed. (1) As the NaO concentration increases in borosilicate glass frit, the K-edge peak of Si shifts to the low energy side. (2) The peak height of the K-edge of Si differs depending on the kind of lanthanide.