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.

Raman spectroscopy of eutectic melting between boride granule and stainless steel for sodium-cooled fast reactors

Fukai, Hirofumi*; Furuya, Masahiro*; Yamano, Hidemasa

Nuclear Engineering and Technology, 55(3), p.902 - 907, 2023/03

https://doi.org/10.1016/j.net.2022.11.010

This paper addresses reaction products and their distribution of the eutectic melting/solidifying reaction of boron carbide (BC) and stainless-steel (SS). The influence of the existence of carbon on the BC-SS eutectic reaction was investigated by comparing the iron boride (FeB)-SS reaction by Raman spectroscopy with Multivariate Curve Resolution (MCR) analysis. The scanning electron microscopy with dispersive X-ray spectrometer was also used to investigate the elemental information of the pure metals such as Cr, Ni, and Fe. In the BC-SS samples, a new layer was formed between BC/SS interface, and the layer was confirmed that the formed layer corresponded to amorphous carbon (graphite) or FeB or FeB. In contrast, a new layer was not clearly formed between FeB and SS interface in the FeB-SS samples.

Structural investigation of borosilicate glasses by using XAFS measurement in soft X-ray region, 2 (Joint research)

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%.

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.

Visualization of the boron distribution in core material melting and relocation specimen by neutron energy resolving method

Abe, Yuta; Tsuchikawa, Yusuke; Kai, Tetsuya; Matsumoto, Yoshihiro*; Parker, J. D.*; Shinohara, Takenao; Oishi, Yuji*; Kamiyama, Takashi*; Nagae, Yuji; Sato, Ikken

JPS Conference Proceedings (Internet), 33, p.011075_1 - 011075_6, 2021/03

https://doi.org/10.7566/JPSCP.33.011075

Structural change of borosilicate glass by boron isotope composition

Nagai, Takayuki; Okamoto, Yoshihiro; Akiyama, Daisuke*; Uehara, Akihiro*; Fujii, Toshiyuki*; Sekimoto, Shun*

KURNS Progress Report 2019, P. 257, 2020/08

https://www.rri.kyoto-u.ac.jp/PUB/report/PR/ProgRep2019/ProgressReport2019_online.pdf

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.

XAFS measurement of simulated waste glass samples (Joint research)

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.

XAFS measurement of simulated waste glass samples prepared from borosilicate glass frit including phosphorus pentaoxide (Joint research)

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

JAEA-Research-2018-005.pdf:28.2MB

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.

XAFS measurement of simulated waste borosilicate glass samples (Joint research)

Nagai, Takayuki; Kobayashi, Hidekazu; Sasage, Kenichi; Ayame, Yasuo; Okamoto, Yoshihiro; Shiwaku, Hideaki; Yamanaka, Keisuke*; Ota, Toshiaki*

JAEA-Research 2017-005, 54 Pages, 2017/06

JAEA-Research-2017-005.pdf:16.17MB

Addition of radioactive waste to a borosilicate frit affects the local structures of boron (B) and waste elements in a waste glass. Synchrotron XAFS measurement was applied to investigate the local structural changes by using simulated waste borosilicate glass samples. Following results were obtained by the B K-edge XAFS analysis. It was confirmed that B K-edge XAFS analysis enables us to discriminate sp type boron (BO) from sp type boron (BO). Addition of waste elements to a glass frit increases the percentage of BO and decreases that of BO. By decreasing the SiO/AlO ratio or increasing the (SiO+BO)/AlO ratio in the glass composition, the BO percentage increases and the BO percentage decreases. Addition of PO decreases the BO percentage and increases the BO percentage. Following results were obtained from XAFS measurement of the waste elements. Cerium (Ce) valence is more reduced with the increase of the BO content. Addition of PO has a tendency to reduce the Ce valence and to enhance deposition of Zr oxide. Deposition of ruthenium compounds separated from glass phase can not be improved by changing the BO content. This study was performed as a part of the project, "Improvement of vitrification process of high-level radioactive liquid wastes" on the foundation business of the Agency for Natural Resources and Energy.

Influence of boron vapor on transport behavior of deposited CsI during heating test simulating a BWR severe accident condition

Sato, Isamu; Onishi, Takashi; Tanaka, Kosuke; Iwasaki, Maho; Koyama, Shinichi

Journal of Nuclear Materials, 461, p.22 - 28, 2015/06

https://doi.org/10.1016/j.jnucmat.2015.02.032

In order to evaluate B influence on the release and transport of Cs and I during severe accidents, basic experiments have been performed on the interaction between deposited Cs/I compounds and vapor/aerosol B compounds. CsI and BO were utilized as a Cs/I compound and a B compound, respectively. Deposited CsI on the thermal gradient tube (TGT), which is exposed to temperatures ranging from 423 K to 1023 K was reacted with vapor/aerosol BO, and then observed to determine how it changed Cs/I decomposition profiles. As a result, vapor/aerosol BO stripped a portion of deposited CsI within a temperature range from 830 K to 920 K to make gaseous CsBO and I. In addition, gaseous I was re-deposited at a temperature range from 530 K to 740 K, while CsBO travelled through the sampling tubes and filters without deposition. It is implied that B influences Cs carriers such as CsBO to transport Cs to the colder regions.