Crystal-liquid duality driven ultralow two-channel thermal conductivity in -MgAgSb

Li, J.*; Li, X.*; Zhang, Y.*; Zhu, J.*; Zhao, E.*; 古府 麻衣子; 中島 健次; Avdeev, M.*; Liu, P.-F.*; Sui, J.*; et al.

Applied Physics Reviews (Internet), 11(1), p.011406_1 - 011406_8, 2024/03

https://doi.org/10.1063/5.0173680

The desire for intrinsically low lattice thermal conductivity () in thermoelectrics motivates numerous efforts on understanding the microscopic mechanisms of heat transport in solids. Here, based on theoretical calculations, we demonstrate that -MgAgSb hosts low-energy localized phonon bands and avoided crossing of the rattler modes, which coincides with the inelastic neutron scattering result. Using the two-channel lattice dynamical approach, we find, besides the conventional contribution (70% at 300 K) from particlelike phonons propagating, the coherence contribution dominated by the wavelike tunneling of phonons accounts for 30% of total at 300 K. By considering dual contributions, our calculated room-temperature of 0.64 WmK well agrees with the experimental value of 0.63 WmK. More importantly, our computations give a nonstandard dependence, perfectly explaining the abnormal temperature-trend of in experiment for -MgAgSb. By molecular dynamics simulation, we reveal that the structure simultaneously has soft crystalline sublattices with the metavalent bonding and fluctuating liquid-like sublattices with thermally induced large amplitude vibrations. These diverse forms of chemical bonding arouse mixed part-crystal part-liquid state, scatter strongly heat-carrying phonons, and finally produce extremely low . The fundamental research from this study will accelerate the design of ultralow- materials for energy-conversion applications.

Proton diffusion in liquid 1,2,3-triazole studied by incoherent quasi-elastic neutron scattering

篠原 佑也*; 岩下 拓哉*; 中西 真大*; Osti, N. C.*; 古府 麻衣子; 楡井 真実; Dmowski, W.*; 江上 毅*

Journal of Physical Chemistry B, 128(6), p.1544 - 1549, 2024/02

https://doi.org/10.1021/acs.jpcb.3c07685

Improving the proton transport in polymer electrolytes impacts the performance of next-generation solid-state batteries. However, little is known about proton conductivity in nonaqueous systems due to the lack of an appropriate level of fundamental understanding. Here, we studied the proton transport in small molecules with dynamic hydrogen bonding, 1,2,3-triazole, as a model system of proton hopping in a nonaqueous environment using incoherent quasi-elastic neutron scattering. By using the jump-diffusion model, we identified the elementary jump-diffusion motion of protons at a much shorter length scale than those by nuclear magnetic resonance and impedance spectroscopy for the estimated long-range diffusion. In addition, a spatially restricted diffusive motion was observed, indicating that proton motion in 1,2,3-triazole is complex with various local correlated dynamics. These correlated dynamics will be important in elucidating the nature of the proton dynamics in nonaqueous systems.

MLFデータ処理環境"空蝉"インストールマニュアル

稲村 泰弘

JAEA-Testing 2023-002, 80 Pages, 2023/12

JAEA-Testing-2023-002.pdf:2.43MB

空蝉とは、J-PARCの物質・生命科学実験施設(MLF)において実施される中性子散乱実験にて得られたデータ処理に使用されるソフトウェア群の一つである。MLFの多くの装置(ビームライン)では、測定されたデータから条件に応じて抽出し、強度の規格化、装置機器依存の強度補正、単位変換などを行い、物理量へと変換し可視化する必要がある。空蝉はこの一連の処理を効率的に行うために開発されたソフトウェア群である。空蝉は主にデータの抽出機能(ヒストグラム化)や各種補正機能、それらを効率よく実行するためのグラフィカルインターフェースを持つソフトウェア、さらには処理されたデータを可視化するプロッタアプリケーションなどから構成されている。既にMLFの多数の装置において解析作業の要として動作している。本書は、MLFの中性子散乱装置を運用する装置担当者やユーザーが空蝉を利用したデータ処理を自分自身の計算機環境にて実施する際に、その環境構築やインストール作業を容易に実施できるよう、オペレーションシステムごとに具体的な手順を記述したマニュアルである。なお、WindowsやmacOSといった一般向けオペレーションシステムであれば、通常のアプリケーションを扱う程度の知識があれば本書を利用してインストールが可能である。

Water fraction dependence of the aggregation behavior of hydrophobic fluorescent solutes in water-tetrahydrofuran

辻 勇人*; 中畑 雅樹*; 菱田 真史*; 瀬戸 秀紀*; 元川 竜平; 井上 大傑*; 江川 泰暢*

Journal of Physical Chemistry Letters (Internet), 14(49), p.11235 - 11241, 2023/12

https://doi.org/10.1021/acs.jpclett.3c02882

This work investigates the water-fraction dependence of the aggregation behavior of hydrophobic solutes in water-tetrahydrofuran (THF) and the elucidation of the role of THF using fluorescence microscopy, dynamic light scattering, neutron and X-ray scattering, as well as photoluminescence measurements. Based on the obtained results, the following model is proposed: hydrophobic molecules are molecularly dispersed in the low-water-content region (10-20 vol %), while they form mesoscopic particles upon increasing the water fraction to 30 vol percent. This abrupt change is due to the composition fluctuation of the water-THF binary system to form hydrophobic areas in THF, followed by THF-rich droplets where hydrophobic solutes are incorporated and form loose aggregates. Further increasing the water content prompts the desolvation of THF, which decreases the particle size and generates tight aggregates of solute molecules. This model is consistent with the luminescence behavior of the solutes and will be helpful to control the aggregation state of hydrophobic solutes in various applications.

Structural changes of polystyrene particles in subcritical and supercritical water revealed by in situ small-angle neutron scattering

柴田 基樹*; 中西 洋平*; 阿部 淳*; 有馬 寛*; 岩瀬 裕希*; 柴山 充弘*; 元川 竜平; 熊田 高之; 高田 慎一; 山本 勝宏*; et al.

Polymer Journal, 55(11), p.1165 - 1170, 2023/11

https://doi.org/10.1038/s41428-023-00817-1

Marine ecosystem degradation due to micro plastics is a significant environmental problem, as acknowledged by Sustainable Development Goal 14. Decomposition of plastics using near critical or supercritical water is one of the promising methods to reduce micro plastics. To attain the optimization of the method for improving environmental friendliness, it is necessary to clarify the structural change of materials during the process. We, thus, investigated the decomposition processes of polystyrene particles dispersed in deuterated water (DO) during heating under near critical or supercritical conditions by using in situ small-angle neutron scattering. Under subcritical conditions, the PS particles were swollen by DO due to increased compatibility with temperature. Near the critical point in subcritical conditions, the cleavage of PS chains in the particles occurred, so that the swollen ratio was much enhanced though the PS particles kept their shapes. In a supercritical condition, the PS particles were degraded into oil including oligomers or monomers and the phase-separated structures with styrene-rich and DO-rich regions.

Preliminary analyses of modified STACY core configuration using serpent with JENDL-5

川口 真穂*; 柴 茂樹*; 岩橋 大希*; 大川 剛*; 郡司 智; 井澤 一彦; 須山 賢也

Proceedings of 12th International Conference on Nuclear Criticality Safety (ICNC2023) (Internet), 8 Pages, 2023/10

原子力規制委員会は、2014年から日本原子力研究開発機構(JAEA)と共同で、福島第一原子力発電所事故で発生した燃料デブリの臨界性を評価するための実験的アプローチに取り組んでいる。その一環として、擬似燃料デブリの特性を評価する臨界実験を実施するため、原子力機構は臨界実験装置STACY(STAtic experiment Critical facilitY)を改良した。予備解析として、提案した炉心配置パターンについて、主要な核データライブラリを用いて臨界特性を検証した。3次元連続エネルギーモンテカルロ中性子・光子輸送コードSERPENT-V2.2.0と最新のJENDL-5を用いた。その結果、STACY更新炉の炉心配置パターン全てにおいてJENDL-5による中性子増倍率は、他のライブラリを使用した結果と比較して大きく評価された。また、JENDL-5のH散乱反応及びU核分裂反応断面積の感度係数は他のライブラリとは異なっていた。これらのライブラリとの比較から、JENDL-5の更新されたS(, )は、STACY更新炉の臨界特性の評価結果に影響を与える可能性があることがわかった。

An X-ray and neutron scattering study of aqueous MgCl solution in the gigapascal pressure range

山口 敏男*; 福山 菜美*; 吉田 亨次*; 片山 芳則*; 町田 真一*; 服部 高典

Liquids, 3(3), p.288 - 302, 2023/09

https://doi.org/10.3390/liquids3030019

圧力0.1MPaから4GPa、温度300Kから500Kにおける2mol/kg MgCl水溶液の構造をX線と中性子散乱測定によって明らかにした。この散乱データを経験的ポテンシャル構造精密化(EPSR)モデリングにより解析し、圧力と温度の関数としてペア分布関数、配位数分布、角度分布、空間密度関数を導出した。Mgは第3殻まで広がったリジッドな溶媒和殻を形成している。つまり、0GPaで約6個の水分子を含む6配位八面体の第1溶媒和殻は、ギガパスカルの圧力領域では、近接イオン対を形成し、約5個の水分子と1個のClとなる。また、Clの溶媒和も、圧力によって大きく変わる。つまり、Clイオンまわりの水分子の配位数は、0.1MPa/300Kでの8から、4GPa/500Kでの10に増加する。また溶媒(水)も、0.1MPa/300Kでの四面体ネットワーク構造から、ギガパスカルの圧力領域では、密に詰まった構造へと変化する。このとき、中心水分子1個まわりの隣接酸素原子数は、0.1MPa/298Kでの4.6個から4GPa/500Kでの8.4個へと徐々に増加する。

Foam flotation of clay particles using a bifunctional amine surfactant

Micheau, C.; 上田 祐生; 元川 竜平; Bauduin, P.*; Girard, L.*; Diat, O.*

Langmuir, 39(31), p.10965 - 10977, 2023/07

https://doi.org/10.1021/acs.langmuir.3c01213

Understanding clay flotation mechanisms has become a major concern because of the increasing level of environmental contamination of soil and ground water by heavy metals and radionuclides. Clays are often used as sorbents for extracting metals in indirect flotation processes but can function simultaneously as defoamers. However, how foam generation and stability depend on the molecular interactions between the clays and surfactant is still controversial. In the present study, an amine polyethoxylated surfactant was used as a bifunctional surfactant that collected clay particles and acted as a foaming agent in the flotation process. The pH conditions strongly affected the surfactant physicochemical properties, allowing the clay extraction efficiency to be tuned. The interfacial recovery factor of the clays almost reached 100 percent under acidic (pH lower than 6) and neutral (pH 6-10) conditions, whereas it was negative under alkaline conditions (pH higher than 10), contrary to expectations. To elucidate the mechanisms involved in the particle flotation process for each of the pH conditions, the bulk and foam phases were analyzed. The effects of electrostatic interactions between the solutes and multiscale structure on the clay extraction behavior were investigated by electrophoretic measurements, dynamic light scattering, small-angle neutron scattering, and image analysis. Based on these results, three flotation processes were found depending on pH range: surfactant foam fractionation at pH higher than 10; clay particle foam flotation at pH 6-10; and particle froth flotation at pH lower than 6.

Differences in water dynamics between the hydrated chitin and hydrated chitosan determined by quasi-elastic neutron scattering

廣田 夕貴*; 富永 大輝*; 川端 隆*; 川北 至信; 松尾 康光*

Bioengineering (Internet), 10(5), p.622_1 - 622_17, 2023/05

https://doi.org/10.3390/bioengineering10050622

Recently, it was reported that chitin and chitosan exhibited high-proton conductivity and function as an electrolyte in fuel cells. In particular, it is noteworthy that proton conductivity in the hydrated chitin becomes 30 times higher than that in the hydrated chitosan. Since higher proton conductivity is necessary for the fuel cell electrolyte, it is significantly important to clarify the key factor for the realization of higher proton conduction from a microscopic viewpoint for the future development of fuel cells. Therefore, we have measured proton dynamics in the hydrated chitin using quasi-elastic neutron scattering (QENS) from the microscopic viewpoint and compared the proton conduction mechanism between hydrated chitin and chitosan. QENS results exhibited that a part of hydrogen atoms and hydration water in chitin are mobile even at 238 K, and the mobile hydrogen atoms and their diffusion increase with increasing temperature. It was found that the diffusion constant of mobile protons is two times larger and that the residence time is two times in chitin faster than that in chitosan. In addition, it is revealed from the experimental results that the transition process of dissociable hydrogen atoms between chitin and chitosan is different. To realize proton conduction in the hydrated chitosan, the hydrogen atoms of the hydronium ions (HO) should be transferred to another hydration water. By contrast, in hydrated chitin, the hydrogen atoms can transfer directly to the proton acceptors of neighboring chitin. It is deduced that higher proton conductivity in the hydrated chitin compared with that in the hydrated chitosan is yielded by the difference of diffusion constant and the residence time by hydrogen-atom dynamics and the location and number of proton acceptors.

Extreme phonon anharmonicity underpins superionic diffusion and ultralow thermal conductivity in argyrodite AgSnSe

Ren, Q.*; Gupta, M. K.*; Jin, M.*; Ding, J.*; Wu, J.*; Chen, Z.*; Lin, S.*; Fabelo, O.*; Rodriguez-Velamazan, J. A.*; 古府 麻衣子; et al.

Nature Materials, 22, p.999 - 1006, 2023/05

https://doi.org/10.1038/s41563-023-01560-x

Ultralow thermal conductivity and fast ionic diffusion endow superionic materials with excellent performance both as thermoelectric converters and as solid-state electrolytes. Yet the correlation and interdependence between these two features remain unclear owing to a limited understanding of their complex atomic dynamics. Here we investigate ionic diffusion and lattice dynamics in argyrodite AgSnSe using synchrotron X-ray and neutron scattering techniques along with machine-learned molecular dynamics. We identify a critical interplay of the vibrational dynamics of mobile Ag and a host framework that controls the overdamping of low-energy Ag-dominated phonons into a quasi-elastic response, enabling superionicity. Concomitantly, the persistence of long-wavelength transverse acoustic phonons across the superionic transition challenges a proposed 'liquid-like thermal conduction' picture. Rather, a striking thermal broadening of low-energy phonons, starting even below 50 K, reveals extreme phonon anharmonicity and weak bonding as underlying features of the potential energy surface responsible for the ultralow thermal conductivity ( 0.5 WmK) and fast diffusion. Our results provide fundamental insights into the complex atomic dynamics in superionic materials for energy conversion and storage.