Long-term changes in the chemical, microstructural, and transport properties of a low-pH cement shotcrete during operation of the Horonobe Underground Research Laboratory, Japan

望月 陽人; 松井 裕哉; 中山 雅; 坂本 亮*; 柴田 真仁*; 本島 貴之*; 城 まゆみ*

Case Studies in Construction Materials, 22, p.e04648_1 - e04648_20, 2025/07

https://doi.org/10.1016/j.cscm.2025.e04648

放射性廃棄物の地層処分で使用される低アルカリ性セメントは、長期にわたる処分場の操業期間中に大気中の二酸化炭素による炭酸化や地下水との接触によってその特性が変化する可能性がある。本研究では、フライアッシュとシリカヒュームを混合した低アルカリ性セメント(HFSC)を用いた吹付けコンクリートの化学的特性、微細構造ならびに輸送特性に対して大気中での炭酸化および地下水との接触が与える影響を、幌延の地下研究施設において16年間にわたり調査した。HFSC吹付けコンクリートの炭酸化領域と溶出領域のいずれにおいても、直径約300nm未満の細孔の毛細管空隙率が増加し、全空隙率は非変質領域よりも高くなった。これらの空隙構造の変化は、ケイ酸カルシウム水和物(C-S-H)の脱灰とエトリンガイトの分解に関連していると考えられる。このような変化は、OPC吹付けコンクリートの変質領域では軽微であったことから、本研究の調査条件下において、HFSC吹付けコンクリートは炭酸化や地下水溶出に対する抵抗性が相対的に低いことが示された。しかしながら、HFSCの透水係数は、地層処分に用いられる低pHセメントに求められる機能要件を満たす程度に低かった。

Achievements and status of the STRAD project for radioactive liquid waste management

荒井 陽一; 渡部 創; 中原 将海; 船越 智雅; 星野 貴紀; 高畠 容子; 坂本 淳志; 粟飯原 はるか; 長谷川 健太; 吉田 稔生; et al.

Progress in Nuclear Science and Technology (Internet), 7, p.168 - 174, 2025/05

https://doi.org/10.15669/pnst.7.168

STRADプロジェクトの進捗に係る報告として、CPFホットセルの処理状況とともに、新たなターゲットに係る研究計画と最新のトピックスについて報告する。

Thinning behavior of solid boron carbide immersed in molten stainless steel for core disruptive accident of sodium-cooled fast reactor

江村 優軌; 高井 俊秀; 菊地 晋; 神山 健司; 山野 秀将; 横山 博紀*; 坂本 寛*

Journal of Nuclear Science and Technology, 61(7), p.911 - 920, 2024/07

https://doi.org/10.1080/00223131.2023.2287109

Boron carbide (BC)- stainless steel (SS) eutectic reaction behavior is one of the most important issues in the core disruptive accidents (CDAs) of sodium-cooled fast reactors (SFRs). In this study, the immersion experiments using BC pellets with molten SS were conducted to evaluate the CDA sequences such as contact event of solid BC with degraded core materials including SS at very high temperature. The immersion experiment aims at understanding the kinetic behavior of solid BC-liquid SS reaction based on the reduced thickness of BC pellet after the experiment in the temperature ranges from 1763 to 1943 K, which is higher than the temperature of solid BC-solid SS reaction. Based on the kinetic consideration of the reaction rate constants for solid BC-liquid SS reaction, it was found that similar temperature dependency was identified between solid BC-liquid SS and solid BC-solid SS. Besides, the reaction rate constants of solid BC-liquid SS were smaller than those of solid BC-solid SS extrapolated in higher temperature region by two or more orders of magnitude due to two different evaluation method for BC side/SS side. It was confirmed that this difference was reasonable through the consideration of previous reaction tests in solid-solid contact for BC side/SS side.

Axial variations of oxide layer growth and hydrogen uptake of BWR fuel claddings under steam starvation conditions

坂本 寛*; Adachi, Mika*; 徳島 二之*; 青見 雅樹*; 柴田 裕樹; 永江 勇二; 倉田 正輝

Zirconium in the Nuclear Industry; 20th International Symposium (ASTM STP 1645), p.411 - 432, 2023/11

https://doi.org/10.1520/STP164520220043

Steam oxidation tests under steam-starved and non-steam-starved conditions were conducted up to 1573 K using prototypic BWR fuel assembly (four fuel pins and fuel channel box) with approximately 750 mm length. Significant suppression of oxide layer growth and enhancement of hydrogen uptake were found at the downstream positions under the steam-starved conditions. To understand the results obtained in the tests using the prototypic BWR fuel assembly, three separate-effects tests were conducted to obtain a fundamental understanding of mechanism of oxygen and hydrogen uptake and its axial variations and evaluation of hydrogen solubility in oxygen-dissolved Zircaloy-2. It is retrieved that the fuel channel box contributes to the axial variations of oxide layer growth and hydrogen uptake of the fuel pins by acting as a source of hydrogen and a sink of oxygen. The evaluation of hydrogen uptake and release requires a detailed estimation of steam oxidation with time at each elevation.

Origin of magnetically dead layers in spinel ferrites FeO grown on AlO; Effects of postdeposition annealing studied by XMCD

野中 洋亮*; 若林 勇希*; 芝田 悟朗; 坂本 祥哉*; 池田 啓祐*; Chi, Z.*; Wan, Y.*; 鈴木 雅弘*; 田中 新*; 田中 雅明*; et al.

Physical Review Materials (Internet), 7(4), p.044413_1 - 044413_10, 2023/04

https://doi.org/10.1103/PhysRevMaterials.7.044413

We study the electronic and magnetic states of as-grown and annealed FeO(111)/AlO3(111) (Co, Ni) thin films with various thicknesses grown on Si(111) substrates with the -AlO(111)buffer layers by using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD), to investigate magnetically dead layers in these films. Although the magnetically dead layers in the as-grown samples are formed near the interface with the AlO buffer layer, we reveal that ferrimagnetic order is partially recovered by postdeposition annealing at 973 K for 48 hours in air. By analyzing the line shapes of the XAS and XMCD spectra, we conclude that, in the dead layers, there are a significant number of vacancies at the sites of the spinel structure, which may be the microscopic origin of the degraded ferrimagnetic order in the FeO thin films.

Lanthanide and actinide ion complexes containing organic ligands investigated by surface-enhanced infrared absorption spectroscopy

平田 早紀子*; 日下 良二; 明地 省吾*; 為国 誠太*; 奥寺 洸介*; 浜田 昇賢*; 坂本 知優*; 本田 匠*; 松下 高輔*; 村松 悟*; et al.

Inorganic Chemistry, 62(1), p.474 - 486, 2023/01

https://doi.org/10.1021/acs.inorgchem.2c03618

A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of diglycolamide (DGA), Cyanex-272, and -tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands. Aqueous solutions of Ln (Eu, Gd, Tb) and An (Am) ions were loaded onto the gold surface to form ion complexes. The IR spectra of the ion complexes were obtained using FT-IR spectroscopy in the attenuated total reflection mode. In this study, we developed a new sample preparation method for SEIRA spectroscopy that enabled us to obtain the IR spectra of the complexes with a small amount of ion solution (5 L). This is a significant advantage for the IR measurement of radiotoxic Am complexes. In the IR spectra of DGA, the band attributed to C=O stretching vibrations at 1630 cm shifted to a lower wavenumber by 20 cm upon complexation with Ln and An ions. Moreover, the amount of the red-shift was inversely proportional to the extraction equilibrium constant reported in previous studies on solvent extraction. The coordination ability of DGA toward Ln and An ions could be assessed using the band position of the C=O band. The Cyanex-272- and TPEN-like ligands synthesized in this report also showed noticeable SEIRA signals for Ln and An complexes. This study indicates that SEIRA spectroscopy can be used for the structural investigation of ion complexes and provides a microscopic understanding of selective extraction of Ln and An.

Roles of excess minority carrier recombination and chemisorbed O species at SiO/Si interfaces in Si dry oxidation; Comparison between p-Si(001) and n-Si(001) surfaces

津田 泰孝; 吉越 章隆; 小川 修一*; 坂本 徹哉*; 山本 善貴*; 山本 幸男*; 高桑 雄二*

Journal of Chemical Physics, 157(23), p.234705_1 - 234705_21, 2022/12

https://doi.org/10.1063/5.0109558

This paper gives experimental evidence for that (1) the excess minority carrier recombination at the SiO/p-Si(001) and SiO/n-Si(001) interfaces is associated with the O dissociative adsorption, (2) the 700-eV X-ray induced enhancement of the SiO growth is not caused by the band flattening due to the surface photovoltaic effect but ascribed to the electron-hole pair creation due to core level photoexcitation for the spillover of the bulk Si electronic states to the SiO layer, (3) changes of band bending result from the excess minority carrier recombination at the oxidation-induced vacancy site when turning on and off the X-ray irradiation, and (4) a metastable chemisorbed O species (Pb1-paul) plays a decisive role in combining two kinds of the reaction loops of single- and double-step oxidation. Based on the experimental results, the unified Si oxidation reaction model mediated by point defect generation [Jpn. J. Appl. Phys. 59, SM0801 (2020)] is extended from a viewpoint of (a) the excess minority carrier recombination at the oxidation-induced vacancy site and (b) the trapping-mediated adsorption through the chemisorbed O species at the SiO/Si interface.

Hybrid process combining solvent extraction / low pressure loss extraction chromatography for a reasonable MA(III) recovery process

佐野 雄一; 坂本 淳志; 宮崎 康典; 渡部 創; 森田 圭介; 江森 達也; 伴 康俊; 新井 剛*; 中谷 清治*; 松浦 治明*; et al.

Proceedings of International Conference on Nuclear Fuel Cycle; Sustainable Energy Beyond the Pandemic (GLOBAL 2022) (Internet), 4 Pages, 2022/07

TBPを利用した溶媒抽出法によるMA(III)+Ln(III)共回収フローシート及び低圧損操作が可能な大粒径多孔質シリカ担体を使用したHONTA含浸吸着材を用いた擬似移動層型クロマトグラフィによるMA(III)/Ln(III)分離フローシートを組み合わせたハイブリッド型のMA(III)回収プロセスを開発した。

大洗研究所における放射性廃棄物の放射能濃度評価手法確立に係る取り組み; 令和2年度活動報告書

朝倉 和基; 下村 祐介; 堂野前 寧; 阿部 和幸; 北村 了一; 宮越 博幸; 高松 操; 坂本 直樹; 磯崎 涼佑; 大西 貴士; et al.

JAEA-Review 2021-020, 42 Pages, 2021/10

JAEA-Review-2021-020.pdf:2.95MB

原子力の研究開発施設から発生する放射性廃棄物の処理処分は、取り扱う核燃料物質や材料が多種多様なこと等を踏まえ、放射能濃度を求める必要がある。大洗研究所は、廃棄物を処理する施設のみならず、廃棄物を発生させる施設も含め、埋設処分を見据えた検討に着手している。本報告書は、大洗研究所内で発生する放射性廃棄物の埋設処分に向けて、主要課題のひとつである放射能濃度評価手法について、令和2年度の検討結果を取りまとめたものである。

Oxidation of anatase TiO(001) surface using supersonic seeded oxygen molecular beam

勝部 大樹*; 大野 真也*; 高柳 周平*; 尾島 章輝*; 前田 元康*; 折口 直紀*; 小川 新*; 池田 夏紀*; 青柳 良英*; 甲谷 唯人*; et al.

Langmuir, 37(42), p.12313 - 12317, 2021/10

https://doi.org/10.1021/acs.langmuir.1c01752

超音速分子ビーム(SSMB)を用いて、アナターゼ型TiO(001)表面の酸素空孔の酸化を調べた。SSMBによって表面およびサブサーフェイスの酸素空孔を除去できた。格子間空孔が酸素空孔の大部分と考えられるが、SSMBによって効果的に除去できた。表面の酸素空孔は、TiO結晶成長後の状態では安定であるが、SSMBを用いて同様に効果的に除去できた。