Phase transitions and relaxor behavior of lead-free ferroelectric bismuth potassium titanate

斎藤 幸太郎*; 松尾 拓紀*; 米田 安宏; Ye, Z.-G*; 野口 祐二*

Journal of Applied Physics, 138(9), p.094102_1 - 094102_9, 2025/09

https://doi.org/10.1063/5.0272995

The phase transition behavior of relaxor ferroelectric BiKTiO (BKT) is investigated in ceramic from based on synchrotron radiation X-ray diffraction measurements and dielectric measurements as a function of temperature. The structural transformation from the cubic non-ergodic (NER) relaxor state to the tetragonal NER state triggers the spontaneous relaxor-to-ferroelectric phase transition. Based on the experimental observations, a temperature phase diagram of BKT is established in terms of average crystal structure and polar order.

Nacre-like MXene/polyacrylic acid layer-by-layer multilayers as hydrogen gas barriers

Auh, Y. H.*; Neal, N. N.*; Arole, K.*; Regis, N. A.*; Nguyen, T.*; 小川 修一*; 津田 泰孝; 吉越 章隆; Radovic, M.*; Green, M. J.*; et al.

ACS Applied Materials & Interfaces, 17(21), p.31392 - 31402, 2025/05

https://doi.org/10.1021/acsami.5c03632

MXenes are a promising class of 2D nanomaterials and are of particular interest for gas barrier application. However, MXene nanosheets naturally bear a negative charge, which prevents assembly with negatively charged polymers, such as polyacrylic acid (PAA), into gas barrier coatings. Here, we present MXene- and PAA-based layer-by-layer (MXene/PAA LbL) multilayers formed by leveraging hydrogen bonding interactions. When assembled in acidic conditions, MXene/PAA LbL films exhibit conformal, pin-hole free, nacre-like structures. The MXene/PAA LbL films yield high blocking capability and low permeability (0.140.01 cc mm m day MPa) for hydrogen gas. These nacre-like structures are also electronically conductive (up to 37030 S cm). Specifically, the reversible deconstruction of these films under basic conditions is experimentally verified. This study shows that hydrogen bonding interactions can be leveraged to form MXene LbL multilayers as gas barriers, electronically conducive coatings, and deconstructable thin films via pH control.

Crystal structures and phase stability of antiferroelectric phases in undoped and Ca-modified sodium niobates

阿蘇 星侑*; 松尾 拓紀*; 米田 安宏; 森川 大輔*; 津田 健治*; 大山 研司*; 石垣 徹*; 野口 祐二*

Physical Review B, 111(17), p.174114_1 - 174114_12, 2025/05

https://doi.org/10.1103/PhysRevB.111.174114

高分解能放射光X線・中性子回折、収束電子線回折、密度汎関数理論(DFT)計算を組合せた解析により、Ca修飾NaNbOと非ドープNaNbOの結晶構造、phase転移、相安定性を調べた。その結果、Ca修飾によって反強誘電体(AFE)-相が200Kから800Kの広い温度範囲で安定化されること、NaNbOは格子膨張を伴う温度誘起等方圧によって安定化されるのに対し、Ca修飾NaNbOは格子収縮を伴う組成誘起化学圧力によって安定化されることが示された。

Germanene reformation from oxidized germanene on Ag(111)/Ge(111) by vacuum annealing

鈴木 誠也; 勝部 大樹*; 矢野 雅大; 津田 泰孝; 寺澤 知潮; 小澤 孝拓*; 福谷 克之; Kim, Y.*; 朝岡 秀人; 柚原 淳司*; et al.

Small Methods, 9(3), p.2400863_1 - 2400863_9, 2025/03

https://doi.org/10.1002/smtd.202400863

For group 14 monoelemental two-dimensional materials, such as silicene, germanene, and stanene, oxidation is a severe problem that alters or degrades their physical properties. This study shows that the oxidized germanene on Ag(111)/Ge(111) can be reformed to germanene by simple heating around 500 C in a vacuum. The key reaction in reforming germanene is the desorption of GeO and GeO during heating around 350 C. After removing surface oxygen, Ge further segregates to the surface, resulting in germanene. The reformed germanene has the same crystal structure, a (7 7) R19.1 supercell with respect to Ag(111), and has equivalent high quality to that of as-grown germanene on Ag(111)/Ge(111). Even after air oxidation, germanene can be reformed by annealing in a vacuum. On the other hand, the desorption of GeO and GeO at high temperatures was not suppressed even in the O backfilling atmosphere. This instability of oxidized germanene/Ag(111)/Ge(111) at high temperatures contributes to the ease of germanene reformation without oxygen. In other words, the present germanene reformation, as well as the segregation of germanene on Ag(111)/Ge(111), is a highly robust process as a synthesis method of germanene.

Sm synchrotron-radiation-based Mssbauer spectroscopy of Sm-based heavy fermion compounds

筒井 智嗣; 東中 隆二*; 水牧 仁一朗*; 小林 義男*; 中村 仁*; 伊藤 孝; 依田 芳卓*; 松田 達磨*; 青木 勇二*; 佐藤 英行*

Interactions (Internet), 245(1), p.9_1 - 9_10, 2024/12

https://doi.org/10.1007/s10751-024-01851-y

Sm synchrotron-radiation-based Mssbauer spectroscopy has been applied to Sm-based heavy fermion intermetallics, SmAl ( = Ti, V and Cr) and SmOsSb. The isomer shifts obtained demonstrate that the Sm valence states in these compounds are intermediate. Since the difference of the isomer shifts in 22.502 keV Sm Mssbauer effect between Sm and Sm state is comparable to the 2nd order Doppler shift, consideration of the 2nd order Doppler shift is required to precisely discuss Sm valence state through the shifts of the Mssbauer spectra. In addition, the plots of the isomer shifts obtained by the Mssbauer spectroscopy against the Sm valence states estimated from Sm L-edge X-ray absorption spectroscopy exhibit a linear correlation except for that in SmOsSb. This implies that the origin of the intermediate valence state in SmOsSb differs from that in SmAl ( = Ti, V and Cr).

Convection and joint characteristics in aluminum alloy melting zone during resistance spot welding of dissimilar Fe-Al material in external magnetic field

船引 雄太*; 伊與田 宗慶*; 菖蒲 敬久; 松田 朋己*; 林 雄二郎*; 佐野 智一*; 他8名*

Journal of Manufacturing Processes, 115, p.40 - 55, 2024/04

https://doi.org/10.1016/j.jmapro.2024.01.049

In resistance spot welding (RSW) of Fe and Al alloy, an intermetallic compound (IMC) is formed at the joining interface, and it is known that the joining strength of the joint decreases as the IMC becomes thicker. In this study, the convection behavior in the Al alloy melting zone of an Fe-Al alloy RSW was varied and the effect on the joint characteristics was investigated. For this study, focusing on the electromagnetic force generated in the Al alloy melting zone, the convection behavior in the Al alloy melting zone was changed by adding an external magnetic field using neodymium magnets. In-situ evaluation of the convection behavior using synchrotron radiation and cross-sectional macro-observation of the joint revealed that the addition of an external magnetic field causes a non-axisymmetric change in the convection behavior in the Al alloy melting zone, which results in the deflection of the Al alloy melting zone. The addition of an external magnetic field increases the driving force of convection and homogenizes the temperature field at the joining interface, suggesting that the IMC near the center is formed thin and uniform. Furthermore, from the cross tension test and the observation of the fracture surface of the joint after the test, it was clarified that the CTS of the joint with an external magnetic field was improved by the propagation of cracks into the Al alloy melting zone during the test.

Stress measurement of stainless steel piping welds by complementary use of high-energy synchrotron X-rays and neutrons

三浦 靖史*; 鈴木 賢治*; 諸岡 聡; 菖蒲 敬久

Quantum Beam Science (Internet), 8(1), p.1_1 - 1_14, 2024/03

https://doi.org/10.3390/qubs8010001

Probabilistic fracture mechanics (PFM) is expected as a reasonable structural integrity assessment method for nuclear components such as piping, whose main degradation phenomenon is stress corrosion cracking (SCC). Some input parameters are necessary for PFM analysis, and welding residual stress is one of the most important parameters because welding residual stress affects SCC initiation and propagation. Recently, a double exposure method (DEM) with synchrotron X-ray has been proposed, and the method is an expected candidate for the measurement of welding residual stress with a high spatial resolution. In this paper, the DEM was applied to measure the residual stress of the plate specimen, which was cut from the welded pipe using electrical discharge machining, and detailed stress maps under a plane stress state were obtained. Furthermore, the residual stress distributions of the welded pipe under a triaxial stress state were also evaluated using neutron diffraction. From these results, the method for obtaining a detailed stress map of the welded pipe by the complementary use of high-energy synchrotron radiation X-rays and neutrons was proposed.

SPring-8 JAEA専用ビームラインBL22XUの設計

塩飽 秀啓; 丸下 元治*

JAEA-Research 2022-015, 39 Pages, 2023/05

JAEA-Research-2022-015.pdf:2.74MB

大型放射光施設SPring-8日本原子力研究所専用ビームライン(現在は、日本原子力研究開発機構(JAEA)専用ビームライン)である硬X線アンジュレータビームラインBL22XUの設計を行った。BL22XUは、主に放射性廃棄物処理に係る分離抽出材の設計及び化学的挙動解明を行うためのXAFS(X-ray Absorption Fine Structure)解析実験、回折計を用いた磁性研究実験、高圧プレスやダイヤモンドアンビルセルを用いた極限環境下実験等を行うためのビームラインである。利用可能なX線エネルギー範囲を370keVに設定した。ビームラインの光学系を設計するために、ミラーの反射率、分光結晶の回折幅、Be窓材の吸収率等を計算した。また、光線追跡を行い、各光学素子の材料、寸法、設置場所等を最適化した。さらに、放射性物質利用上の安全確保のため音響遅延管ADL(Acoustic Delay Line)の遅延時間についても検討を行った。BL22XU「重元素科学研究I」は、2002年にビームラインの建設を終え、立ち上げ調整期間を経て、既に運用している。軟X線アンジュレータを光源とするもう一つのJAEA専用ビームラインBL23SU「重元素化科学究II」と共に、2つのビームラインを相補的に利用することによって、原子力科学が直面する多くの問題を解決する放射光ビームラインとして発展することが期待されている。2018年から2019年に分光器の高度化を実施したため、ビームライン建設当時の設計、特徴と性能を改めてここに記録することとした。

Relationship between internal stress distribution and microstructure in a suspension-sprayed thermal barrier coating with a columnar structure

山崎 泰広*; 篠宮 啓介*; 奥村 忠晴*; 鈴木 賢治*; 菖蒲 敬久; 中村 唯我*

Quantum Beam Science (Internet), 7(2), p.14_1 - 14_12, 2023/05

https://doi.org/10.3390/qubs7020014

The suspension plasma spray (SPS) technique has attracted attention because of its various microstructures, which can be achieved by mixing submicron spray particles with a solvent to form a suspension. Thermal barrier coatings (TBCs) with a columnar structure, which might achieve high strain tolerance, can be obtained using the SPS technique. In this study, the internal stress distribution of the SPS-TBC with different columnar structures was evaluated by hybrid measurement using high-energy synchrotron X-ray diffraction analysis and laboratory low-energy X-rays. The effect of microstructure on the internal stress distribution of the SPS-TBC was discussed on the basis of the experimental results. In addition, the in-plane internal stress was decreased by decreasing the column diameter. The thin columnar microstructure of the SPS-TBC has superior strain tolerance. The internal stresses in the column of the SPS-TBC are periodic decrements caused by stress relaxation in porous layers.

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.