Neutron diffraction study of the crystal and magnetic structures of antiferromagnetic manganese deuteride at high temperatures and high pressures

Machida, Akihiko*; Saito, Hiroyuki*; Aoki, Katsutoshi*; Komatsu, Kazuki*; Hattori, Takanori; Sano, Asami; Funakoshi, Kenichi*; Machida, Shinichi*; Sato, Toyoto*; Orimo, Shinichi*

Physical Review B, 111(22), p.224413_1 - 224413_6, 2025/06

https://doi.org/10.1103/yf8k-cy61

The crystal and magnetic structures of antiferromagnetic Mn deuterides formed by hydrogenating Mn metal at high temperature and high pressure, fcc -MnDx and hcp -MnDx, were investigated by in-situ neutron powder diffraction. Deuterium atoms partially occupied the octahedral interstitial positions of the fcc and hcp metal lattices. The site occupancies increased rapidly with decreasing temperature from 700 to 450 K and remained down to 300 K. Nel temperature of 543(10) K was determined for -MnD. For -MnD, saturation magnetic moment and Nel temperature were determined to be 0.82(1) and 347(3) K, respectively. The Nel temperatures determined for -MnD and -MnD are consistent with those predicted by the respective Slater-Pauling curves proposed in previous studies. The updated Nel temperatures provide insights into the development of more accurate Slater-Pauling curves based on electronic band structure calculations.

Determination of Sr in highly radioactive aqueous samples via conversion to a kinetically stable 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid complex followed by concentration-separation-fractionation based on capillary electrophoresis-liquid scintillation

Ouchi, Kazuki; Haraga, Tomoko; Hirose, Kazuki*; Kurosawa, Yuika*; Sato, Yoshiyuki; Shibukawa, Masami*; Saito, Shingo*

Analytica Chimica Acta, 1298, p.342399_1 - 342399_7, 2024/04

https://doi.org/10.1016/j.aca.2024.342399

Given that conventional methods of high-dose sample analysis pose substantial exposure risks and generate large amounts of secondary radioactive waste, faster procedures allowing for decreased radiation emission are highly desirable. To address this need, we developed a Sr quantitation technique that is based on liquid scintillation counting-coupled capillary transient isotachophoresis (ctITP) with two-point detection and relies on the rapid concentration, separation, and fractionation of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-complexed Sr in a single run. This method, which allows for the handling of high-dose radioactive specimens at the microliter level and is substantially faster than conventional ion-exchange protocols, was used to selectively quantify Sr in real high-dose waste. The successful concentration-separation in ctITP was ascribed to the inertness of the Sr-DOTA complex to dissociation.

Slightly hydrogen-ordered state of ice IV evidenced by neutron diffraction

Kobayashi, Hiroki*; Komatsu, Kazuki*; Ito, Hayate*; Machida, Shinichi*; Hattori, Takanori; Kagi, Hiroyuki*

Journal of Physical Chemistry Letters (Internet), 14(47), p.10664 - 10669, 2023/11

https://doi.org/10.1021/acs.jpclett.3c02563

Ice IV is a metastable high-pressure phase of ice in which the water molecules exhibit orientational disorder. Although orientational ordering is commonly observed for other ice phases, it has not been reported for ice IV. We conducted powder neutron diffraction experiments for DCl-doped DO ice IV to investigate hydrogen ordering in ice IV. We found abrupt changes in the temperature derivative of unit cell volume, dV/dT, at about 120 K, and revealed their slightly ordered structure at low temperatures based on the Rietveld method. The occupancy of the D1 site deviates from 0.5; it increased when samples were cooled at higher pressures and reached 0.282(5) at 2.38 GPa, 58 K. Our results evidence the presence of a low-symmetry hydrogen-ordered state corresponding to ice IV. It seems, however, difficult to experimentally access the completely ordered phase corresponding to ice IV by slow cooling at high pressure.

Spontaneous topological Hall effect induced by non-coplanar antiferromagnetic order in intercalated van der Waals materials

Takagi, Hirotaka*; Takagi, Rina*; Minami, Susumu*; Nomoto, Takuya*; Oishi, Kazuki*; Suzuki, Michito*; Yanagi, Yuki*; Hirayama, Motoaki*; Khanh, N.*; Karube, Kosuke*; et al.

Nature Physics, 19(7), p.961 - 968, 2023/07

https://doi.org/10.1038/s41567-023-02017-3

Americium(III)/curium(III) complete separation and sensitive fluorescence detection by capillary and gel electrophoresis using emissive hexadentate/octadentate polyaminocarboxylate ligands

Saito, Shingo*; Haraga, Tomoko; Marumo, Kazuki*; Sato, Yoshiyuki; Nakano, Yuta*; Tasaki-Handa, Yuiko*; Shibukawa, Masami*

Bulletin of the Chemical Society of Japan, 96(3), p.223 - 225, 2023/03

https://doi.org/10.1246/bcsj.20220346

Highly efficient and effective separation between americium (Am) and curium ion (Cm) was achieved by two simple electrophoresis-based techniques. Am and Cm ions were complexed with fluorophore-modified acyclic hexadentate and octadentate polyaminocarboxylates and then were electrophoretically separated and fluorescently detected in free solution with ternary complexation or in gel medium.

Unusually kinetically inert monocationic neptunyl complex with a fluorescein-modified 1,10-phenanthroline-2,9-dicarboxylate ligand; Specific separation and detection in gel electrophoresis

Yamagata, Kazuhito*; Ouchi, Kazuki; Marumo, Kazuki*; Tasaki-Handa, Yuiko*; Haraga, Tomoko; Saito, Shingo*

Inorganic Chemistry, 62(2), p.730 - 738, 2023/01

https://doi.org/10.1021/acs.inorgchem.2c02908

The inert NpO complex with a fluorescein-modified phenanthroline-2,9-dicarboxylic acid was found by kinetic selection using polyacrylamide gel electrophoresis (PAGE) from a small chemical library. The small spontaneous dissociation rate constant of 810 s (the half-life of 23 hours) was determined. This is the singly-charged NpO complex exhibiting unusual kinetic inertness in aqueous solution, one million times slower than widely accepted fast kinetics of neptunyl complexes. Selective fluorescence detection of NpO was achieved in PAGE with a detection limit of 68 pmol dm(17 fg). This system was successfully applied to simulated spent nuclear fuel and high-level radioactive waste samples.

Volatilization of BC control rods in Fukushima Daiichi nuclear reactors during meltdown; B-Li isotopic signatures in cesium-rich microparticles

Fueda, Kazuki*; Takami, Ryu*; Minomo, Kenta*; Morooka, Kazuya*; Horie, Kenji*; Takehara, Mami*; Yamasaki, Shinya*; Saito, Takumi*; Shiotsu, Hiroyuki; Onuki, Toshihiko*; et al.

Journal of Hazardous Materials, 428, p.128214_1 - 128214_10, 2022/04

https://doi.org/10.1016/j.jhazmat.2022.128214

Annual report on the environmental radiation monitoring around the Tokai Reprocessing Plant FY2020

Nakada, Akira; Nakano, Masanao; Kanai, Katsuta; Seya, Natsumi; Nishimura, Shusaku; Nemoto, Masashi; Tobita, Keiji; Futagawa, Kazuo; Yamada, Ryohei; Uchiyama, Rei; et al.

JAEA-Review 2021-062, 163 Pages, 2022/02

JAEA-Review-2021-062.pdf:2.87MB

Environmental radiation monitoring around the Tokai Reprocessing Plant has been performed by the Nuclear Fuel Cycle Engineering Laboratories, based on "Safety Regulations for the Reprocessing Plant of Japan Atomic Energy Agency, Chapter IV - Environmental Monitoring". This annual report presents the results of the environmental monitoring and the dose estimation to the hypothetical inhabitant due to the radioactivity discharged from the plant to the atmosphere and the sea during April 2020 to March 2021. In this report, some data include the influence of the accidental release from the Fukushima Daiichi Nuclear Power Station of Tokyo Electric Power Co., Inc. (the trade name was changed to Tokyo Electric Power Company Holdings, Inc. on April 1, 2016) in March 2011. Appendices present comprehensive information, such as monitoring programs, monitoring methods, monitoring results and their trends, meteorological data and discharged radioactive wastes. In addition, the data which were influenced by the accidental release and exceeded the normal range of fluctuation in the monitoring, were evaluated.

Origin of magnetovolume effect in a cobaltite

Miao, P.*; Tan, Z.*; Lee, S. H.*; Ishikawa, Yoshihisa*; Torii, Shuki*; Yonemura, Masao*; Koda, Akihiro*; Komatsu, Kazuki*; Machida, Shinichi*; Sano, Asami; et al.

Physical Review B, 103(9), p.094302_1 - 094302_18, 2021/03

https://doi.org/10.1103/PhysRevB.103.094302

The layered perovskite PrBaCoO demonstrates a strong negative thermal expansion (NTE) which holds potential for being fabricated into composites with zero thermal expansion. The NTE was found to be intimately associated with the spontaneous magnetic ordering, known as magneto-volume effect (MVE). Here we report with compelling evidences that the continuous-like MVE in PrBaCoO is intrinsically of discontinuous character, originating from an magnetoelectric transition from an antiferromagnetic insulating large-volume (AFILV) phase to a ferromagnetic less-insulating small-volume (FLISV) phase. Furthermore, the magnetoelectric effect (ME) shows high sensitivity to multiple external stimuli such as temperature, carrier doping, hydrostatic pressure, magnetic field etc. In contrast to the well-known ME such as colossal magnetoresistance and multi-ferroic effect which involve symmetry breaking of crystal structure, the ME in the cobaltite is purely isostructural. Our discovery provides a new path way to realizing the ME as well as the NTE, which may find applications in new techniques.

Experimental evidence for the existence of a second partially-ordered phase of ice VI

Yamane, Ryo*; Komatsu, Kazuki*; Gochi, Jun*; Uwatoko, Yoshiya*; Machida, Shinichi*; Hattori, Takanori; Ito, Hayate*; Kagi, Hiroyuki*

Nature Communications (Internet), 12, p.1129_1 - 1129_6, 2021/02

https://doi.org/10.1038/s41467-021-21351-9

Ice exhibits extraordinary structural variety in its polymorphic structures. The existence of a new form of diversity in ice polymorphism has recently been debated in both experimental and theoretical studies, questioning whether hydrogen-disordered ice can transform into multiple hydrogen-ordered phases, contrary to the known one-to-one correspondence between disordered ice and its ordered phase. Here we report a new high-pressure phase, ice XIX, which is a second hydrogen-ordered phase of ice VI. This is the first discovery to demonstrate that disordered ice undergoes different manners of hydrogen ordering. Such multiplicity can appear in all disordered ice, and it widely provides a new research approach to deepen our knowledge, for example of the crucial issues of ice: the centrosymmetry of hydrogen-ordered configurations and potentially induced (anti-)ferroelectricity. Ultimately, this research opens up the possibility of completing the phase diagram of ice.