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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
FeUO, CrUO
, and Fe
Cr
UO
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 Fe
Cr
UO
was composed of a uranyl-like structure in its lattice regardless of its "x"' value. M
ssbauer measurements indicated that the Fe in FeUO
and Fe
Cr
UO
were trivalent. Furthermore, Fe
Cr
UO
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 FexCr
UO
effectively suppressed the decomposition of the Fe
Cr
UO
crystal, even at a very low Cr content.
Motokawa, Ryuhei; Kaneko, Koji; Oba, Yojiro; Nagai, Takayuki; Okamoto, Yoshihiro; Kobayashi, Taishi*; Kumada, Takayuki; Heller, W. T.*
Journal of Non-Crystalline Solids, 578, p.121352_1 - 121352_7, 2022/02
Nagai, Takayuki; Okamoto, Yoshihiro; Yamagishi, Hirona*; Ota, Toshiaki*; Kojima, Kazuo*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
JAEA-Research 2021-010, 62 Pages, 2022/01
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 Na
O 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.
Nagai, Takayuki; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Okamoto, Yoshihiro
2020-Nendo "Busshitsu, Debaisu Ryoiki Kyodo Kenkyu Kyoten" Oyobi "Hito, Kankyo To Busshitsu O Tsunagu Inobeshion Soshutsu Dainamikku, Araiansu" Kenkyu Seika, Katsudo Hokokusho (CD-ROM), 1 Pages, 2021/11
no abstracts in English
Okamoto, Yoshihiro; Kobayashi, Hidekazu; Shiwaku, Hideaki; Sasage, Kenichi; Hatakeyama, Kiyoshi*; Nagai, Takayuki
Journal of Non-Crystalline Solids, 551, p.120393_1 - 120393_8, 2021/01
Times Cited Count:0 Percentile:0.02(Materials Science, Ceramics)The chemical state of ruthenium in simulated iron phosphate radioactive waste glass was investigated by conventional X-ray absorption fine structure (XAFS) and imaging XAFS analyses. The EXAFS analysis suggested that ruthenium was contained as glass phase when content of the waste components was less than 10wt.% in 30 mol%FeO
-P
O
base glass. In other samples, crystalline RuO
was predominant. According to the imaging XAFS analysis, RuO
particles in all samples had length smaller than 50
m. Aggregations of RuO
, which are found in nuclear waste borosilicate glass, were not seen in any of the iron phosphate glass samples.
Nagai, Takayuki; Akiyama, Daisuke*; Kirishima, Akira*; Sato, Nobuaki*; Okamoto, Yoshihiro
2019-Nendo "Busshitsu, Debaisu Ryoiki Kyodo Kenkyu Kyoten" Oyobi "Hito, Kankyo To Busshitsu O Tsunagu Inobeshion Soshutsu Dainamikku, Araiansu" Kenkyu Seika, Katsudo Hokokusho (CD-ROM), P. 20191107_1, 2020/11
no abstracts in English
Nagai, Takayuki; Okamoto, Yoshihiro; Yamagishi, Hirona*; Ota, Toshiaki*; Kojima, Kazuo*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
JAEA-Research 2020-009, 48 Pages, 2020/09
The local structure of glass-forming elements and waste elements in waste glass 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), and waste elements of cerium (Ce), 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 existence ratio of four coordinate sp structure (BO
) tends to increase with increasing Na
O content in glass samples. (2) The height of a pre-edge which appears by K-edge XANES spectrum of O is so high that the Fe content in glass samples. Following results were obtained by XAFS measurements of simulated waste glass samples after immersion test to investigate long chemical stability. (1) The existence ratio of four coordinate sp
structure (BO
) increases by immersion test. (2) Ce which exists in the surface layer is oxidized by immersion test, and much of Cs in surface layer is lost after leach testing. Even if the glass frit form (fiber cartridge or beads) and manufacturing method were changed and a glass sample of the similar chemical composition was prepared, these observed Raman spectra of samples were different.
Nagai, Takayuki; Okamoto, Yoshihiro; Akiyama, Daisuke*; Uehara, Akihiro*; Fujii, Toshiyuki*; Sekimoto, Shun*
KURNS Progress Report 2019, P. 257, 2020/08
To understand the influence of glass structural change by neutron irradiation and boron isotope composition, glass samples were made from enrichment boric acid reagents and neutron irradiation of those samples was carried out in Pn-2 of KUR. The structural change of glass sample after the irradiation will be estimated in 2020FY. Before neutron irradiation test of glass samples, the Si-O bridging structure difference by boron isotope composition compared by using a Raman spectrometry.
Nagai, Takayuki; Shimoyama, Iwao; Okamoto, Yoshihiro; Akiyama, Daisuke*; Arima, Tatsumi*
Photon Factory Activity Report 2019 (Internet), 3 Pages, 2020/00
no abstracts in English
Nagai, Takayuki; Sasage, Kenichi; Okamoto, Yoshihiro; Shiwaku, Hideaki; Yamagishi, Hirona*; Ota, Toshiaki*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*; Takahashi, Tomoe*; et al.
JAEA-Research 2019-003, 94 Pages, 2019/09
The local structures of glass-forming elements and waste elements would change by the chemical composition of waste glass including those elements. In this study, simulated waste glass samples were prepared from borosilicate glass frit including phosphorus (P) or vanadium (V), and we investigated local structures of boron, sodium, and waste elements in these P glass and V glass samples by using synchrotron XAFS measurements in soft and hard X ray region.
Nagai, Takayuki; Kobayashi, Hidekazu; Okamoto, Yoshihiro; Akiyama, Daisuke*; Sato, Nobuaki*; Uehara, Akihiro*; Fujii, Toshiyuki*; Sekimoto, Shun*
KURNS Progress Report 2018, P. 105, 2019/08
To understand this structural change of a borosilicate glass by a neutron irradiation in detail, the irradiation test was carried out in KUR in 2017FY. The glass structure was estimated by using Raman spectrometry in 2018FY. Comparing with the Raman spectra of glass samples before and after irradiation, it could be observed the change of peak height of Si-O bridging structure by the irradiation.
Nagai, Takayuki; Akiyama, Daisuke*; Sato, Nobuaki*; Okamoto, Yoshihiro
"Busshitsu, Debaisu Ryoiki Kyodo Kenkyu Kyoten" Oyobi "Hito, Kankyo To Busshitsu O Tsunagu Inobeshion Soshutsu Danamikku, Araiansu" Kenkyu Seika, Katsudo Hokokusho (Heisei-30-Nendo) (CD-ROM), P. 20181080_1, 2019/06
no abstracts in English
Okamoto, Yoshihiro; Nagai, Takayuki; Shiwaku, Hideaki; Kano, Shigeru; Himeno, Haruyuki*; Kobayashi, Hiroshi*; Nakatani, Mikio*
JAEA-Research 2018-013, 18 Pages, 2019/03
The chemical state and local structure of some elements in the simulated nuclear waste glass samples (20 batches) prepared by bottom drain test in the full scale mock-up tests using KMOC melter were investigated by synchrotron radiation based X-ray absorption fine structure (XAFS) analysis. As a result of the analysis of cerium element, it was confirmed that the oxidation proceeds gently as the batch advanced. For manganese, iron, and zinc, there was almost no difference between batches, which seemed to be stabilized by getting into the frame structure of the borosilicate glass. There were no elements that seemed to be clearly crystalline except for platinum group elements. Remarkable precipitation was hardly observed in zirconium and molybdenum with the imaging analysis.
Okamoto, Yoshihiro; Nagai, Takayuki; Shiwaku, Hideaki
Yoyuen Oyobi Koon Kogaku, 62(1), p.11 - 17, 2019/01
The vitrified radioactive waste is a multicomponent material containing many kinds of elements. Synchrotron radiation XAFS with element selectivity is suitable for analysis of elements in the waste. From the XAFS analysis, the chemical state and the local structure of each element were clarified. Imaging XAFS technique was used as an analysis based on element distribution in the glass. The imaging XAFS is effective for analysis of elements that are less soluble in the glass like molybdenum and platinum group elements. It was clarified from the simultaneous imaging XAFS analyses of multiple elements that the chemical form of rhodium is strongly dominated by the distribution correlation with ruthenium. We proposed multi - scale structural analyses with wide angle scattering, PDF analysis, small angle scattering in order to evaluate the soundness of the vitrified waste.
Nagai, Takayuki; Okamoto, Yoshihiro; Akiyama, Daisuke*; Sato, Nobuaki*
Photon Factory Activity Report 2018 (Internet), 2 Pages, 2019/00
no abstracts in English
Nagai, Takayuki; Okamoto, Yoshihiro; Shiwaku, Hideaki; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*; Hirono, Kazuya*; Homma, Masanobu*; Kobayashi, Hiromi*; Takahashi, Tomoe*; et al.
JAEA-Research 2018-007, 87 Pages, 2018/11
To select the chemical composition of a glass frit which can increase the waste content, the simulated waste glass samples prepared from a borosilicate glass frit including vanadium (V) were investigated by using Laser Ablation (LA) ICP-AES analysis, Raman spectrometry, and synchrotron XAFS measurement in this study on foundation business of the Agency for Natural Resources and Energy.
Nagai, Takayuki; Kobayashi, Hidekazu; Shimamura, Keisuke; Oyama, Koichi; Sasage, Kenichi; Okamoto, Yoshihiro; Shiwaku, Hideaki; Yamanaka, Keisuke*; Ota, Toshiaki*
JAEA-Research 2018-005, 72 Pages, 2018/09
Addition of radioactive waste to a borosilicate glass frit affects the local structures of glass-forming elements and waste elements in a waste glass produced in a vitrification process. In this study, simulated waste glass samples were prepared from borosilicate glass frit including phosphorus pentaoxide, and we investigated local structures of sodium (Na), boron (B), and waste elements in these glass samples by using synchrotron XAFS measurements in soft and hard X ray region.
Nagai, Takayuki; Uehara, Akihiro*; Fujii, Toshiyuki*
KURRI Progress Report 2017, P. 128, 2018/08
In this study, to understand the structural change of a borosilicate glass by a neutron irradiation in detail, the neutron irradiation test was carried out for 50 min in the Pn-2 of the Kyoto University Research Reactor (KUR). The structural change of glass sample after the irradiation will be estimated in 2018FY. Before the irradiation test, the glass composition was selected to estimate a structural change accurately by Raman spectrometry and 2 kinds of Li free borosilicate glass for the irradiation test samples were prepared.
Okamoto, Yoshihiro; Nagai, Takayuki; Shiwaku, Hideaki
Hoshako, 31(4), p.274 - 280, 2018/07
As a method for disposal of nuclear waste, the use of vitrification technique is very promising. In this technique, many kinds of elements should be involved stably in the glass and chemical state of these elements in the glass must be confirmed in order to guarantee stability of the glass. We have used synchrotron based X-ray absorption fine structure (XAFS) technique, in which the element selectivity is utilized, to obtain the chemical state of each element in many kinds of simulated glass samples. In addition, imaging XAFS technique has been used to clarify correlation between constituent elements. We are going to contribute to research and development of the vitrification technique by using synchrotron radiation based XAFS analyses. In this article, we introduce results of the high energy XAFS of high temperature slag samples, the imaging study of high temperature borosilicate glass samples and the imaging XAFS analysis of platinum group metals in the borosilicate glass samples.
Nagai, Takayuki; Akiyama, Daisuke*; Sato, Nobuaki*
Busshitsu, Debaisu Ryoiki Kyodo Kenkyu Kyoten Kenkyu Seika Hokokusho (Heisei-29-Nendo) (CD-ROM), 1 Pages, 2018/04
no abstracts in English