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.

Investigation of chemical state of uranium included in simulated waste glass

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), 20181080_1 Pages, 2019/06

no abstracts in English

Contribution to upgrade of vitrification technology by synchrotron radiation analysis; From Chemical state analysis of waste glass to development of structural analysis to prove soundness

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.

Chemical state analysis of simulated corium debris by EXAFS

Okamoto, Yoshihiro; Takano, Masahide

Progress in Nuclear Science and Technology (Internet), 5, p.200 - 203, 2018/11

https://doi.org/10.15669/pnst.5.200

Chemical state of some simulated corium debris samples containing uranium (fuel), zirconium (fuel cladding), iron (structure material), calcium (cement) and lanthanides (fission products) was investigated by synchrotron radiation based extended X-ray absorption fine structure (EXAFS) analysis. The local structure of uranium for the simulated debris was classified into fluorite UO structure and C-type structure (stabilized cubic). The UZrFeCaO sample, which consists of single phase (C-type), shows slightly shorter U-O distance. It can be concluded that the sample contains pentavalent uranium. The local structure of zirconium for U-Zr-O and U-Zr-Fe-O systems was very close to tetragonal ZrO, while that of zirconium changed to CSZ (calcia stabilized cubic) by adding calcium.

Synchrotron radiation based X-ray absorption study for upgrade of nuclear waste vitrification technique

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.

Study on Mo structure in simulated dissolved solutions of activated metal waste

Shimada, Asako; Okamoto, Yoshihiro

Photon Factory Activity Report 2017, 2 Pages, 2018/00

http://pfwww.kek.jp/acr/2017pdf/u_reports/pf17b0191.pdf

no abstracts in English

The Significance of bromide in the Brust-Schiffrin synthesis of thiol protected gold nanoparticles

Booth, S. G.*; Uehara, Akihiro*; Chang, S.-Y.*; La Fontaine, C.*; Fujii, Toshiyuki*; Okamoto, Yoshihiro; Imai, Takahito*; Schroeder, S. L. M.*; Dryfe, R. A. W.*

Chemical Science, 8(12), p.7954 - 7962, 2017/12

https://doi.org/10.1039/C7SC03266H

The two-phase Brust-Schiffrin synthesis of alkane thiol protected metal nanoparticles has been shown to undergo significantly different processes dependent on the precursor species and reactant conditions. In this work X-ray absorption spectroscopy is used in conjunction with liquid/liquid electrochemistry in order to highlight the significance of Br; to the reaction mechanism. We propose that the observed behavior of [AuBr]; species described herein explain a deviation in reported behavior present in the current literature. The reported mechanistic understanding should enable a nanoparticle synthesis with a higher yield and reduce size polydispersity.

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.

Development of cesium-free mineralization for decontamination and reuse of radioactive contaminated soil in Fukushima

Shimoyama, Iwao; Honda, Mitsunori; Kogure, Toshihiro*; Baba, Yuji; Hirao, Norie*; Okamoto, Yoshihiro; Yaita, Tsuyoshi; Suzuki, Shinichi

Photon Factory News, 35(1), p.17 - 22, 2017/05

http://pfwww.kek.jp/publications/pfnews/35_1/saikin2.pdf

We introduce Cs-free mineralization (CFM) for Cs removal and reuse of radioactive-contaminated soil in Fukushima and report recent work conducted in the BL27A beamline in Photon Factory. In this work, we investigated compositional and structural changes of Cs-sorbed weathered biotite (WB) before and after heating treatment with addition of NaCl-CaCl salts under low-pressure condition, to study Cs desorption mechanism from clay minerals. X-ray fluorescence spectroscopy clarified that almost all Cs and K were removed with the salts at 700 C. On the other hand, Ca increased with heating temperature. X-ray diffraction and transmission electron microscopy analysis clarified that phase transitions from WB to some Ca-rich silicate minerals, e.g., augite, were caused by the heating treatment with the salt. Based on these results, CFM is proposed for Cs removal utilizing the mechanism in which large monovalent cations are discharged with accompanying the phase transition. We also discuss the role of Cl in this reaction showing chemical bonding change of Cl observed using X-ray absorption spectroscopy in the early stage of the chemical reaction.

Local structure analysis of ZrN, and DyZyN surrogate materials for fast reactor nitride fuel

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

Transactions of the Materials Research Society of Japan, 42(2), p.23 - 26, 2017/04

ZnN is a possible candidate for the diluent material for nitride fuels containing transuranium elements. Pellets of inert matrix material ZrN, and surrogate nitride fuel material DyZrN, are fabricated for the purpose of investigating the crystal structure. Lattice parameters of DyZrN followed the Vegard's low, in spite of the large lattice mismatch ( 7%) between DyN and ZrN. Local structure analysis was performed by X-ray absorption fine structure (XAFS) and atomic pair-distribution function (PDF) methods. The Zr-N nearest neighbor bond distance changed as changing the Dy composition. The complex local structure of DyN and ZrN is related to the preferable effects of ZrN.