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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
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.
Nagai, Takayuki; Okamoto, Yoshihiro; Yamagishi, Hirona*; Kojima, Kazuo*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
JAEA-Research 2022-008, 37 Pages, 2022/10
JAEA-Research-2022-008.pdf:5.27MB
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 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. Following results were obtained by XAFS measurements of simulated waste glass surfaces after immersion test to investigate the long chemical stability. (1) As the leaching time of glass samples in immersion test passed, the Cs M
, M
-edge XANES spectra disappeared and the Fe L
, L
-edge spectra changed. (2) A new compound was formed on the sample surface after the immersion test, and these changes in the surface state were confirmed by Raman spectroscopy. However, it became difficult to obtain a clear B K-edge XANES spectrum by forming a compound on glass surfaces. The Si K-edge XANES spectra of borosilicate glass frits with different NaO content 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 intensity of the Si K-edge peak is maximum when the NaO content in glass frits was about 7wt%.
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.
Nagai, Takayuki; Okamoto, Yoshihiro; Yamagishi, Hirona*; Ota, Toshiaki*; Kojima, Kazuo*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
JAEA-Research 2020-009, 48 Pages, 2020/09
JAEA-Research-2020-009.pdf:4.53MB
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 NaO 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; 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
JAEA-Research-2019-003.pdf:7.92MB
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; 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
JAEA-Research-2018-007.pdf:61.21MB
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.
Okamoto, Yoshihiro; Nagai, Takayuki; Shiwaku, Hideaki; Inose, Takehiko*; Sato, Seiichi*
Nihon Genshiryoku Gakkai Wabun Rombunshi, 16(4), p.180 - 190, 2017/12
X-ray absorption fine structure (XAFS) and imaging XAFS analyses were performed to elucidate chemical state of rhodium in the simulated waste glass. The chemical forms of Rh in the glass were evaluated to be 84% RhO and 16% metal/alloy as the result of linear combination analysis of EXAFS data. According to the imaging XAFS analysis, the chemical form of Rh which was located together with Ru was mainly oxide (RhO). It suggests that stable (Ru,Rh)O solid solution exists in the simulated glass. On the other hand, that of Rh of which distribution did not accord with Ru in the glass was mainly metallic. In the case of metallic Rh in the glass, it tended to become an aggregation form. It can be concluded that the chemical state of Rh was much affected by the existence and distribution of Ru element.
Inose, Takehiko*; Nishizawa, Daiji; Oyama, Koichi; Miyauchi, Atsushi; Nagai, Takayuki
no journal, ,
no abstracts in English
Oyama, Koichi; Inose, Takehiko*; Miyauchi, Atsushi; Nishizawa, Daiji*; Nagai, Takayuki
no journal, ,
no abstracts in English
Nagai, Takayuki; Sasage, Kenichi; Oyama, Koichi; Sato, Nobuaki*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
no journal, ,
no abstracts in English
Inose, Takehiko*; Nishizawa, Daiji*; Miyauchi, Atsushi; Oyama, Koichi; Yamakawa, Atsushi*; Nagai, Takayuki
no journal, ,
no abstracts in English
Inose, Takehiko*; Oyama, Koichi; Miyauchi, Atsushi; Nishizawa, Daiji*; Nagai, Takayuki
no journal, ,
no abstracts in English
Nagai, Takayuki; Kobayashi, Hidekazu; Okamoto, Yoshihiro; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*; Seki, Katsumi*
no journal, ,
no abstracts in English
Nagai, Takayuki; Sasage, Kenichi; Oyama, Koichi; Sato, Nobuaki*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
no journal, ,
no abstracts in English
Okamoto, Yoshihiro; Nagai, Takayuki; Inose, Takehiko*; Sato, Seiichi*; Shiwaku, Hideaki
no journal, ,
The imaging XAFS measurements of Ru and Rh elements was performed to investigate distribution, chemical state and correlation between the two elements in the simulated borosilicate glass samples. According to the analysis of Rh elements, it was concluded that the chemical form in the aggregated area was metallic, while that in other area was mainly RhO
. In addition, it can be seen that the chemical form of Rh tends to be RhO, in the area where a lot of Ru is distributed.
generation by reaction with Ru-La-Na mix nitrates and raw materials for vitrificationNagai, Takayuki; Kobayashi, Hidekazu; Okamoto, Yoshihiro; Sato, Nobuaki*; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*; Seki, Katsumi*
no journal, ,
It is thought that a generated ruthenium compound grows from a high level radioactive liquid waste into RuO crystal by reacting to raw materials for the vitrification process. In this study, the generation reaction to RuO was confirmed by heating Ru-La-Na mix nitrates and the raw materials.
meltNagai, Takayuki; Okamoto, Yoshihiro; Inose, Takehiko*; Akiyama, Daisuke*; Sato, Nobuaki*
no journal, ,
A supplied high level liquid waste into the glass melter is formed to the mixed nitrate salt after the dehydration. In this study, NaNO which is a main ingredient in the waste was selected by the solvent, and NaNO sample including Ru was prepared, and the redox behavior of Ru in NaNO melt was measured by the Cyclic Voltammetry. And valence of Ru included in solidified salt was estimated by the synchrotron XAFS measurement.
Okamoto, Yoshihiro; Nagai, Takayuki; Kobayashi, Hidekazu; Oyama, Koichi; Sasage, Kenichi; Shiwaku, Hideaki; Inose, Takehiko*; Sato, Seiichi*
no journal, ,
The local structures around some elements in newly developed nuclear waste glass simulation samples using phosphorus-doped borosilicate glass and iron phosphate glass as frit were investigated by synchrotron radiation based XAFS analysis. It was found that the addition of phosphorus to borosilicate glass changes the glass to a significant reduction state and counteract oxidation effects induced by increasing waste loading. In iron phosphate glass with a composition of 30% FeO-PO
, the XAFS analysis results showed that the solubility of ruthenium could reach 0.5-1.0%.
Nagai, Takayuki; Sasage, Kenichi; Inose, Takehiko*; Sato, Seiichi*; Hatakeyama, Kiyoshi*
no journal, ,
no abstracts in English
Nagai, Takayuki; Kobayashi, Hidekazu; Sasage, Kenichi; Oyama, Koichi; Sato, Seiichi*; Inose, Takehiko*; Hatakeyama, Kiyoshi*
no journal, ,
We estimated the long chemical stability of simulated waste borosilicate glass samples reacting with water in a closed case by the immersion test in alkaline solution and confirmed the effect which restrains the elution of molybdenum to the solution from the glass samples made with the frit including phosphorus. After cooling the simulated waste glass samples from melt condition, the crystallization behavior in the glass samples made with the frit including phosphorus was confirmed similar to that of the sample made with a present frit composition.
