Organization of malonamides from the interface to the organic bulk phase

Micheau, C.; 上田 祐生; 元川 竜平; 阿久津 和宏*; 山田 悟史*; 山田 雅子*; Moussaoui, S. A.*; Makombe, E.*; Meyer, D.*; Berthon, L.*; et al.

Journal of Molecular Liquids, 401, p.124372_1 - 124372_12, 2024/05

https://doi.org/10.1016/j.molliq.2024.124372

Supramolecular organization of extractant molecules impacts metal ions separation behavior. Probing bulk and interfacial structures of the relevant systems is expected to provide key insights into the metal ion selectivity and kinetic aspects. The supramolecular features of two solvent extraction systems based on malonamide extractants, N,N,N′,N′-tetrahexylmalonamide (THMA) in toluene and N,N′-dimethyl-N,N′-dibutyl-2-tetradecylmalonamide (DBMA) in n-heptane, were studied using small-angle X-ray scattering for the organic bulk phases, as well as interfacial tension and neutron reflectivity measurements for the interfaces. In the bulk solution, THMA forms dimeric/trimeric associates but no aggregates in toluene, while DBMA forms large aggregates in n-heptane. On the other hand, THMA accumulates in a diffuse layer at the interface at high THMA concentration, whereas DBMA forms a compact but thinner layer. After Pd(II) extraction, the thickness of interfacial layers decreases in the case of THMA, and totally vanishes in the case of DBMA. Based on these new structural information, two mechanisms are proposed for Pd(II) and Nd(III) extraction with malonamides. In toluene, THMA associates slightly accumulate in the vicinity of the interface, then coordinate Pd(II) and diffuse into the organic bulk phase. In n-heptane, DBMA aggregates adsorb at the interface then pick up Nd(III) cations in their polar cores and finally diffuse into the bulk.

、、X線同時解析による迅速・高感度放射性核種分析法の開発(委託研究); 令和4年度英知を結集した原子力科学技術・人材育成推進事業

廃炉環境国際共同研究センター; 日本分析センター*

JAEA-Review 2023-022, 93 Pages, 2023/12

JAEA-Review-2023-022.pdf:4.7MB

日本原子力研究開発機構(JAEA)廃炉環境国際共同研究センター(CLADS)では、令和4年度英知を結集した原子力科学技術・人材育成推進事業(以下、「本事業」という。)を実施している。本事業は、東京電力ホールディングス株式会社福島第一原子力発電所の廃炉等を始めとした原子力分野の課題解決に貢献するため、国内外の英知を結集し、様々な分野の知見や経験を、従前の機関や分野の壁を越えて緊密に融合・連携させた基礎的・基盤的研究および人材育成を推進することを目的としている。平成30年度の新規採択課題から実施主体を文部科学省からJAEAに移行することで、JAEAとアカデミアとの連携を強化し、廃炉に資する中長期的な研究開発・人材育成をより安定的かつ継続的に実施する体制を構築した。本研究は、令和2年度に採択された研究課題のうち、「、、X線同時解析による迅速・高感度放射性核種分析法の開発」の令和2年度から令和4年度分の研究成果について取りまとめたものである。本研究は、燃料デブリ・廃棄物中放射性核種の迅速分析の実現を目指し、多重線検出法などの最新計測システムを整備し、スペクトル定量法(Spectral Determination Method:以下、「SDM法」という。)を開発する。令和4年度の研究においては、令和3年度に引き続き、LSC、シングルスGe、2Dスペクトル(多重)の測定データを統一的に扱うコードを開発するとともに、40核種のそれぞれの測定におけるスペクトルデータを実測およびシミュレーション計算により求め、統合データベースを整備した。粗化学分離法については、最終的に7分離法-12ステップを経由し、10個のフラクションとすることで、39核種の定量が可能であることがわかった。SDM法はスペクトル分析一般に適用できるため、今後広い分野への応用が期待される。また、SDM法の高精度化のため、畳み込みニューラルネットワーク(CNN)を用いた複数核種の核種識別法を本研究で対象とする全核種について対応を行った。

Deformation mechanism of a strong and ductile maraging steel investigated using X-ray synchrotron diffraction

Li, H.*; Liu, Y.*; Zhao, W.*; Liu, B.*; 冨永 亜希; 菖蒲 敬久; Wei, D.*

International Journal of Plasticity, 165, p.103612_1 - 103612_20, 2023/06

https://doi.org/10.1016/j.ijplas.2023.103612

コバルトフリーのマルエージング鋼の強度特性を明らかにするために、高エネルギー放射光X線回折法を利用したその場引張試験を行った。マルテンサイト相とオーステナイト相からの回折プロファイルが得られ、それらの強度及び幅が負荷に伴い変化している様子が観察された。回折プロファイルを解析した結果、時効(as-aged)材では、低応力レベルにてマルテンサイトの含有量が緩やかに減少し、高応力レベルでは急激に減少した。一方、熱処理(as-solution)材では、応力の増加とともにオーステナイト相がマルテンサイト相に著しく転移変態している結果が得られた。これらのことがそれぞれの強度特性に起因していることを明らかにした。

A Study on convection in molten zone of aluminum alloy during Fe/Al resistance spot welding

伊與田 宗慶*; 松田 朋己*; 佐野 智一*; 茂田 正哉*; 菖蒲 敬久; 湯本 博勝*; Koyama, Takahisa*; Yamazaki, Hiroshi*; 仙波 泰徳*; 大橋 治彦*; et al.

Journal of Manufacturing Processes, 94, p.424 - 434, 2023/05

https://doi.org/10.1016/j.jmapro.2023.03.032

Aluminum alloys are increasingly being applied to automobile bodies to reduce the weight of automobiles. In joining steel materials and aluminum alloys using resistance spot welding (RSW), it is important to control the state of intermetallic compounds due to the temperature at the joining interface. In other words, in RSW of Fe/Al dissimilar materials, it is necessary to clarify the heating and cooling phenomena of the interface temperature during joining. Although the convection behavior of the molten aluminum alloy is thought to influence the temperature distribution at the joining interface, there are no studies that have directly observed this phenomenon. In this study, convection in molten zone of aluminum alloy during RSW of steel and aluminum alloy is discussed. Direct observations were attempted in order to clarify the convection behavior of the molten aluminum alloy in RSW of steel and aluminum alloy. The main feature of this experiment is that a real-scale test piece and an RSW apparatus used in actual production were used to observe convection during actual production. The observation experiments were conducted using synchrotron radiation X-ray at SPring-8. During welding, the specimens were irradiated with synchrotron radiation X-ray, and convection was observed from the behavior of tracer particles placed on the specimens. As a results, three types of convection were observed: radial outward convection from the center of the molten zone at the joining interface, convection from the edge of the molten zone toward its center, and weak circulating convection at the edge of the molten zone. And, small convection velocities were generated at the edge of the molten zone. Furthermore, the convection velocity inside the molten zone was calculated to be approximately 1.75 m/s. In addition, it was shown that there is a correlation between convection behavior and the shape of the molten zone.

Automatic object recognition using deep learning for legacy waste treatment

吉田 幸彦

IL Nuovo Cimento, 46(2), p.33_1 - 33_8, 2023/03

https://doi.org/10.1393/ncc/i2023-23033-x

JAEA is addressing the back-end issues with the steadfast promotion of sustainable measures. The R&D plans are being rationally pursued by considering priorities based on indicators such as bottleneck issues in waste streams, relevance to WAC settings, and effectiveness of cost reduction. In addition, the future vision (JAEA 2050+) has been formulated to promote cross-disciplinary R&D through a new approach that cannot be reached by conventional methods, and active incorporation of information technologies, such as AI technologies. Currently, we are developing intelligent sensing that combines sensing and information processing technologies to realize automatic sorting technology, and non-destructive evaluation technology using high-energy X-ray CT, for legacy wastes. The core technology common to these technologies is image evaluation technology using deep learning models, which was confirmed to perform very well in the evaluation of waste object recognition.

Insight on the mechanical properties of hierarchical porous calcium-silicate-hydrate pastes according to the Ca/Si molar ratio using synchrotron X-ray scattering and nanoindentation test

Im, S.*; Jee, H.*; Suh, H.*; 兼松 学*; 諸岡 聡; Choe, H.*; 西尾 悠平*; 町田 晃彦*; Kim, J.*; Lim, S.*; et al.

Construction and Building Materials, 365, p.130034_1 - 130034_18, 2023/02

https://doi.org/10.1016/j.conbuildmat.2022.130034

Nanocrystalline calcium-silicate-hydrate (C-S-H) is a typical heterogeneous material with a multiscale structure spanning a wide length scale from angstrom to micrometer, and whose structure is determined by the Ca/Si ratio. In this study, we directly applied compressive loads on synthetic C-S-H pastes with Ca/Si ratios of 0.6-1.2 and investigated their mechanical properties using the elastic modulus calculated at three length scale levels (i.e., angstrom to nanometer, micrometer, and millimeter) via in-situ synchrotron X-ray scattering, nanoindentation tests, and strain gauges, respectively. Further, Si nuclear magnetic resonance spectroscopy was conducted on the C-S-H pastes to elucidate the alterations in the silicate polymerization. The experimental results confirmed the deformation behavior of the C-S-H paste with different Ca/Si ratios under external loading, which was demonstrated to be transferred from the surface of the pastes to particles owing to the presence of multiscale pores.

Effect of magnesium silicate hydrate (M-S-H) formation on the local atomic arrangements and mechanical properties of calcium silicate hydrate (C-S-H); In situ X-ray scattering study

Kim, G.*; Im, S.*; Jee, H.*; Suh, H.*; Cho, S.*; 兼松 学*; 諸岡 聡; 小山 拓*; 西尾 悠平*; 町田 晃彦*; et al.

Cement and Concrete Research, 159, p.106869_1 - 106869_17, 2022/09

https://doi.org/10.1016/j.cemconres.2022.106869

This study explored the effect of M-S-H formation on the local atomic arrangements and mechanical properties of C-S-H. The elastic moduli of the samples were calculated using shifted atomic distances (r) and d-spacings (d) acquired by applying an external load on the pastes during X-ray scattering experiments. The experimental results indicated that the crystal structure of C-S-H remained intact with MgCl addition. At the highest Mg/Si ratio (Ca/Si = 0.6, Mg/Si = 0.2), change in the dominant phase occurred from C-S-H to M-S-H because the low pH environment hindered the formation of C-S-H and facilitated the formation of M-S-H. The elastic modulus decreased with increasing Mg/Si ratio up to 0.1 owing to both C-S-H destabilization and low M-S-H content in the samples. Conversely, the elastic modulus increased in the paste synthesized with the highest Mg/Si ratio because considerable M-S-H had formed, which exhibited a higher elastic modulus than C-S-H.

Study on the relation between the crystal structure and thermal stability of FeUO and CrUO

秋山 大輔*; 日下 良二; 熊谷 友多; 中田 正美; 渡邉 雅之; 岡本 芳浩; 永井 崇之; 佐藤 修彰*; 桐島 陽*

Journal of Nuclear Materials, 568, p.153847_1 - 153847_10, 2022/09

https://doi.org/10.1016/j.jnucmat.2022.153847

ウラン酸鉄,ウラン酸クロム、およびその固溶体を合成し、これらのウラン酸塩が異なる熱的安定性を示すメカニズムを研究した。熱的安定性を評価するため、ウラン酸塩試料の熱重量分析を実施した結果、ウラン酸クロムの分解温度(約1250C)に対してウラン酸鉄は低温(約800C)で分解するが、クロムを含む固溶体では熱分解に対する安定性が高まることが分かった。この熱的安定性と結晶構造との関係性を調べるため、エックス線結晶構造解析,エックス線吸収微細構造測定,メスバウアー分光測定,ラマン分光分析による詳細な結晶構造と物性の評価を行ったが、本研究で用いたウラン酸塩試料の間に明瞭な差異は観測されなかった。そのため、熱的安定性の違いは結晶構造に起因するものではなく、鉄とクロムとの酸化還元特性の違いによるものと推定した。クロムは3価が極めて安定であるのに対して、鉄の原子価は2価と3価を取ることができる。このため、ウラン酸鉄の場合には結晶中でウランと鉄との酸化還元反応が起こり、低温での分解反応を誘起したものと考えられる。

Influence of distant scatterer on air kerma measurement in the evaluation of diagnostic X-rays using Monte Carlo simulation

富永 正英*; 永安 結花里*; 佐々木 幹治*; 古田 琢哉; 林 裕晃*; 笈田 将皇*; 西山 祐一*; 芳賀 昭弘*

Radiological Physics and Technology, 14(4), p.381 - 389, 2021/12

https://doi.org/10.1007/s12194-021-00641-3

放射線診断技術の発展により、患者の被ばく線量の増大が問題となっており、医療被ばくの最適化を目的として、日本国内で共通の診断参考レベルが策定された。この中で、X線一般撮影については、患者の体表面における線量を各施設の診断線量レベルとして評価することが推奨されている。体表面の線量は、体内部からの後方散乱を表す係数を機器設置やメンテナンス等で測られる空中空気カーマに乗じることで、簡便に導出できる。しかし、障害物からの距離を十分取れない状況では、測定される空中空気カーマへ散乱X線が混入するため、線量評価の誤差の要因となる。そこで、モンテカルロシミュレーション計算により、散乱体の物質や距離が散乱X線へ与える影響を評価した。診断X線のエネルギー領域では、軽元素と重元素で散乱に関する物理現象が異なり、物質毎にX線の照射野やエネルギーへの依存性が変化することがわかった。また、どの物質でも35cm程度の距離を取れば、散乱X線の混入をほぼ無視できることがわかった。

A Multi-technique tomography-based approach for non-invasive characterization of additive manufacturing components in view of vacuum/UHV applications; Preliminary results

Grazzi, F.*; Cialdai, C.*; Manetti, M.*; Massi, M.*; Morigi, M. P.*; Bettuzzi, M.*; Brancaccio, R.*; Albertin, F.*; 篠原 武尚; 甲斐 哲也; et al.

Rendiconti Lincei. Scienze Fisiche e Naturali, 32(3), p.463 - 477, 2021/09

https://doi.org/10.1007/s12210-021-00994-2

In this paper, we have studied an additively manufactured metallic component, intended for ultra-high vacuum application, the exit-snout of the MACHINA transportable proton accelerator beam-line. Metal additive manufacturing components can exhibit heterogeneous and anisotropic microstructures. Two non-destructive imaging techniques, X-ray computed tomography and Neutron Tomography, were employed to examine its microstructure. They unveiled the presence of porosity and channels, the size and composition of grains and intergranular precipitates, and the general behavior of the spatial distribution of the solidification lines. While X-ray computed tomography evidenced qualitative details about the surface roughness and internal defects, neutron tomography showed excellent ability in imaging the spatial density distribution within the component. The anisotropy of the density was attributed to the material building orientation during the 3D printing process. Density variations suggest the possibility of defect pathways, which could affect high vacuum performances. In addition, these results highlight the importance of considering building orientation in the design for additive manufacturing for UHV applications.