Durability of U-Zr oxide solid solution in aqueous HO solution

Kumagai, Yuta; Kusaka, Ryoji; Takano, Masahide; Watanabe, Masayuki

Journal of Nuclear Materials, 625, p.156553_1 - 156553_7, 2026/04

https://doi.org/10.1016/j.jnucmat.2026.156553

Uranium-zirconium oxide solid solution, (U, Zr)O, is a representative matrix phase found in fuel debris formed during severe nuclear reactor accidents. Understanding its chemical behavior in oxidative aqueous environments is important for evaluating the potential release of radionuclides during water contact. In this study, we investigated the reactivity of (U, Zr)O with hydrogen peroxide (HO) in pure water to assess its resistance to oxidative dissolution, because HO is the dominant oxidant produced by water radiolysis. The dissolution behavior of uranium and zirconium was monitored through repeated HO exposure experiments, and the solid phases were characterized using Raman micro-spectroscopy and X-ray diffraction. Kinetic modeling was performed to interpret experimental data. The results showed that uranium dissolution occurred initially but decreased significantly upon repeated HO exposure, while zirconium dissolution proceeded more slowly. Raman analysis revealed only minor surface changes, with limited formation of uranyl peroxide phases. The kinetic simulation reproduced the experimental trends by assuming a small fraction of redox-active surface sites. These findings suggest that the observed durability of (U, Zr)O against HO-induced oxidative dissolution is not due to the formation of a protective surface layer, but rather reflects the limited redox reactivity of most of the surface. This study provides a quantitative basis for understanding the HO-induced oxidation of (U, Zr)O in water, relevant to the long-term behavior of fuel debris.

Clarification of debris formation conditions on the basis of the sampling data and experimental study using simulated fuel debris and reinforcement of the analytical results of severe accident scenario (Contract research); FY2023 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; University of Fukui*

JAEA-Review 2025-007, 120 Pages, 2025/09

JAEA-Review-2025-007.pdf:8.13MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2023. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station (1F), Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2021, this report summarizes the research results of the "Clarification of debris formation conditions on the basis of the sampling data and experimental study using simulated fuel debris and reinforcement of the analytical results of severe accident scenario" conducted from FY2021 to FY2023. The present study aims to clarify the debris formation mechanism and utilize the results to refine the accident scenario. In the backward analysis of oxide debris formation, we prepared simulated fuel particles by the aerodynamic levitation method and ejection of melted oxides from a tungsten pipe with a small hole and summarized the relationship between preparation conditions and the properties of the particles. We also demonstrated the formation of simulated fuel debris obtained by the sampling in 1F and clarified the difference between the experimental results and thermodynamic calculation. From the estimation of mixing, melting and solidified states of metallic debris, it was found that the formation of thin reaction layer suppresses the damage of SUS in spite of Zr content around 1000 C, and we quantify the elution rate of BC and Zircaloy to the melted SUS. We extended reaction rate data between various pressure vessel with SUS and Zr and welding parts and suggested reaction rate equation for large scale experiment. We also estimated the failure behavior of lower plenum of pressure vessel and outflow behavior of melt. Furthermore, we estimated transition behavior of Uranium melt to metallic debris melt in the re-melting process of predropped metallic debris. As the experimental techniques in the future, we prepared the semi-melted debris from oxide and metals and analyzed the reaction products and discussed the formation of simulated debris with a small amount of uranium oxide using a CCIM furnace and the aerodynamic levitation method.

Clarification of debris formation conditions on the basis of the sampling data and experimental study using simulated fuel debris and reinforcement of the analytical results of severe accident scenario (Contract Research); FY2022 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; University of Fukui*

JAEA-Review 2024-014, 112 Pages, 2024/08

JAEA-Review-2024-014.pdf:8.22MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2022. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station (1F), Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2021, this report summarizes the research results of the "Clarification of debris formation conditions on the basis of the sampling data and experimental study using simulated fuel debris and reinforcement of the analytical results of severe accident scenario" conducted in FY2022. The present study aims to clarify the debris formation mechanism and utilize the results to refine the accident scenario. In the backward analysis of oxide debris formation, we succeeded in the formation of simulated fuel particle by the aerodynamic levitation method and ejection of melted oxides from tungsten pipe with a small hole. And we demonstrated the formation of simulated fuel debris of U1-No.15 obtained by the sampling in 1F.

Structure, stability, and actinide leaching of simulated nuclear fuel debris synthesized from UO, Zr, and stainless-steel

Kirishima, Akira*; Akiyama, Daisuke*; Kumagai, Yuta; Kusaka, Ryoji; Nakada, Masami; Watanabe, Masayuki; Sasaki, Takayuki*; Sato, Nobuaki*

Journal of Nuclear Materials, 567, p.153842_1 - 153842_15, 2022/08

https://doi.org/10.1016/j.jnucmat.2022.153842

To understand the chemical structure and stability of nuclear fuel debris consisting of UO, Zr, and Stainless Steel (SUS) generated by the Fukushima Daiichi Nuclear Power Plant accident in Japan in 2011, simulated debris of the UO-SUS-Zr system and other fundamental component systems were synthesized and characterized. The simulated debris were synthesized by heat treatment for 1 to 12 h at 1600C, in inert (Ar) or oxidative (Ar + 2% O) atmospheres. Np and Am tracers were doped for the leaching tests of these elements and U from the simulated debris. The characterization of the simulated debris was conducted by XRD, SEM-EDX, Raman spectroscopy, and Mssbauer spectroscopy, which provided the major uranium phase of the UO -SUS-Zr debris was the solid solution of UO (s.s.) with Zr(IV) and Fe(II) regardless of the treatment atmosphere. The long-term immersion test of the simulated debris in pure water and that in seawater revealed the macro scale crystal structure of the simulated debris was chemically very stable in the wet condition for a year or more. Furthermore, the leaching test results showed that the actinide leaching ratios of U, Np, Am from the UO-SUS-Zr debris were very limited and less than 0.08 % for all the experiments in this study.

Basic research on the stability of fuel debris including alloy phase (Contract research); FY2019 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; Tohoku University*

JAEA-Review 2020-032, 97 Pages, 2021/01

JAEA-Review-2020-032.pdf:4.16MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2019. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station, Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2018, this report summarizes the research results of the "Basic Research on the Stability of Fuel Debris Including Alloy Phase" conducted in FY2019. In the present study, we focus on fuel debris consisting of oxide phase and alloy phase generated by the high-temperature chemical reaction between structure materials (SUS pipes, pressure vessels, etc.) and fuels (melted fuels, claddings components, etc.). We synthesize the simulated debris of UO-SUS system and UO-Zr(ZrO)-SUS system by high-temperature heat treatment, and measure their chemical property and dissolution behavior in water. Also, we will conduct research and development to spectroscopically analyze secular changes of oxide phase and alloy phase in the simulated debris.

Chlorination of UO and (U,Zr)O solid solution using MoCl

Sato, Takumi; Shibata, Hiroki; Hayashi, Hirokazu; Takano, Masahide; Kurata, Masaki

Journal of Nuclear Science and Technology, 52(10), p.1253 - 1258, 2015/10

https://doi.org/10.1080/00223131.2015.1070110

In order to explore the applicability of the chlorination by MoCl as a potential pretreatment technique for waste treatment of fuel debris by pyrochemical methods, chlorination experiments of UO and (UZr)O simulated fuel debris were carried out in two steps: the first one is a chlorination reaction by homogeneous heating, the second one is a volatilization of molybdenum by-product by heating under temperature gradient condition. Most of UO and (UZr)O powder were converted to UCl or UCl and ZrCl mixture at 573 K, respectively. In the case of (UZr)Osintered particle, most of sample was converted to the chlorides because the products evaporated and be separated from sample surface at 773 K, while only the surface of the sample disk was converted to the chlorides at 573 and 673 K. Most of molybdenum by-product and ZrCl were separated from UCl by volatilization at 573 K.

Experiment and analysis on in-vessel debris coolability in ALPHA program

Maruyama, Yu; ; Moriyama, Kiyofumi; H.S.Park*; Kudo, Tamotsu; Y.Yang*; Sugimoto, Jun

JAERI-Conf 98-009, p.100 - 106, 1998/00

https://jopss.jaea.go.jp/pdfdata/JAERI-Conf-98-009.pdf

no abstracts in English

Studies on in-vessel debris coolability in ALPHA program

Maruyama, Yu; Yamano, N.; Moriyama, Kiyofumi; H.S.Park*; Kudo, Tamotsu; Sugimoto, Jun

NUREG/CP-0157, 2, p.161 - 172, 1996/00

no abstracts in English

Characterization of melt-solidified (U, Gd, Zr)O as simulated corium debris

Morimoto, Kyoichi; Hirooka, Shun; Akashi, Masatoshi; Watanabe, Masashi

no journal, , 

The influence of Gd on characteristics of debris is important for removing the debris from the reactors of Fukushima Daiichi Nuclear Power Plant because subassemblies of nuclear fuels containing GdO were loaded in the some reactor cores. Additionally, it is important to assess the distribution state of Gd from the anxiety of re-criticality caused by the relocation of debris while removing them. In this study, sintered pellets of (UGdZr)O (y=0,0.5, 2-x=1.989-2.000) were melted and solidified to prepare specimens of simulated corium debris. Phase states and fundamental properties of them were evaluated.

The Possible use of short half-life noble gas fission products for measurement of criticality and identification of plutonium in fuel debris canister

Riyana, E. S.; Okumura, Keisuke; Sakamoto, Masahiro; Matsumura, Taichi; Terashima, Kenichi

no journal, ,