Hydroxyl group/fluorine disorder in deuterated magnesium hydroxyfluoride and behaviors of hydrogen bonds under high pressure

He, X.*; Kagi, Hiroyuki*; Komatsu, Kazuki*; Iizuka, Riko*; Okajima, Hajime*; Hattori, Takanori; Sano, Asami; Machida, Shinichi*; Abe, Jun*; Goto, Hirotada*; et al.

Journal of Molecular Structure, 1310, p.138271_1 - 138271_8, 2024/08

https://doi.org/10.1016/j.molstruc.2024.138271

High-pressure responses of the O-DF hydrogen bonds in deuterated magnesium hydroxyfluoride were investigated using neutron powder diffraction and Raman spectroscopy. The Rietveld analysis at ambient conditions revealed a chemical formula of Mg(OD)F and hydroxyl group/fluorine disorder (OD/F disorder) in the crystal structure, which gave rise to two hydrogen-bonding configurations. The Rietveld analysis showed the hydrogen-bonding geometries remains up to 9.8 GPa, indicating no pressure-induced strengthening of hydrogen bonds. The Raman spectra at ambient conditions showed three hydroxyl stretching bands at 2613, 2694, and 2718 cm. The high frequencies of the O-D stretching modes indicated that the hydroxyls should be involved in weak or none hydrogen-bonding interactions. Up to 20.2 GPa, the mode initially centered at 2694 cm displayed a pressure-induced blue shift, revealing no strengthening of hydrogen bonds under compression. We discuss the existence of hydrogen bonds and the causes of the blue-shifting hydroxyls at ambient and at high pressures.

Stable hydrogen and oxygen isotope analyses of geological samples using a thermal conversion elemental analyzer-isotope ratio mass spectrometer at Tono Geoscience Center

Yamamoto, Yusuke*; Watanabe, Takahiro; Niwa, Masakazu; Shimada, Koji

JAEA-Testing 2023-003, 67 Pages, 2024/02

JAEA-Testing-2023-003.pdf:4.63MB

A long-term geosphere stability for geological disposal is evaluated by the past geological environmental changes and modern conditions. Stable hydrogen and oxygen isotope ratios (D, O) of geological samples are useful information to estimate the past environmental changes and modern conditions. Recently, the thermal conversion elemental analyzer and isotope ratio mass spectrometer (TC-EA/IRMS) were installed in the Tono Geoscience Center for D and O measurements of geological samples. In this study, we reported analytical methods of D and O using international standard reference materials. In addition, evaluation tests of uncertainty by repeated analyses of the standards were performed using the TC-EA/IRMS. Furthermore, the D and O analyses by the TC- EA/IRMS were also applied to fault rock samples.

Stress corrosion cracking induced by the combination of external and internal hydrogen in Al-Zn-Mg-Cu alloy

Tang, J.*; Wang, Y.*; Fujihara, Hiro*; Shimizu, Kazuyuki*; Hirayama, Kyosuke*; Ebihara, Kenichi; Takeuchi, Akihisa*; Uesugi, Masayuki*; Toda, Hiroyuki*

Scripta Materialia, 239, p.115804_1 - 115804_5, 2024/01

https://doi.org/10.1016/j.scriptamat.2023.115804

Stress corrosion cracking (SCC) behaviors induced by the combination of external and internal hydrogen (H) in an Al-Zn-Mg-Cu alloy were systematically investigated via in situ 3D characterization techniques. SCC of the Al-Zn-Mg-Cu alloy could initiate and propagate in the potential crack region where the H concentration exceeded a critical value, in which the nanoscopic H-induced decohesion of -MgZn precipitates resulted in macroscopic cracking. External H that penetrated the alloy from the environment played a crucial role during the SCC of the Al-Zn-Mg-Cu alloy by generating gradient-distributed H-affected zones near the crack tips, which made Al alloys in water environment more sensitive to SCC. Additionally, the pre-existing internal H was driven toward the crack tips during plastic deformation. It was involved in the SCC and made contributions to both the cracks initiation and propagation.

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.

Operation status of the J-PARC high-intensity RF-driven negative hydrogen ion source

Shinto, Katsuhiro; Okoshi, Kiyonori; Shibata, Takanori*; Nammo, Kesao*; Kawai, Isao*; Ikegami, Kiyoshi*; Ueno, Akira

Proceedings of 20th Annual Meeting of Particle Accelerator Society of Japan (Internet), p.928 - 931, 2023/11

https://www.pasj.jp/web_publish/pasj2023/proceedings/PDF/FRP3/FRP35.pdf

J-PARC initiated the operation of the high-intensity rf-driven negative hydrogen (H) ion source in 2014 autumn. The ion source produces the H beam with the beam current of 60 mA and the beam energy of 50 keV in order to inject the H beam into the 3 GeV RCS with the beam current of 50 mA and the beam energy of 400 MeV from the J-PARC linac. We have achieved the longest continuous operation time of 4001 hours in the previous (2021/2022) campaign. The 2022/2023 campaign was the first time that the continuous operation of the H ion source without any exchanges of the ion source until the end of the campaign was examined. We present the operation status of the J-PARC H ion source in this campaign as well as the status of the J-PARC-made internal antenna test.

Development of coupling technology for high temperature gas-cooled reactors and hydrogen production facility; HTTR heat application test project plan

Ishii, Katsunori; Morita, Keisuke; Noguchi, Hiroki; Aoki, Takeshi; Mizuta, Naoki; Hasegawa, Takeshi; Nagatsuka, Kentaro; Nomoto, Yasunobu; Shimizu, Atsushi; Iigaki, Kazuhiko; et al.

Dai-27-Kai Doryoku, Enerugi Gijutsu Shimpojiumu Koen Rombunshu (Internet), 4 Pages, 2023/09

https://doi.org/10.1299/jsmepes.2023.27.A242

Hydrogen isotope separation by quantum tunneling of hydrons through graphene

Yasuda, Satoshi; Dio, W. A.*; Fukutani, Katsuyuki

Vacuum and Surface Science, 66(9), p.514 - 519, 2023/09

https://doi.org/10.1380/vss.66.514

Monolayer graphene, representative of atomically thin crystals, has recently shown unexpectedly high proton and deuteron permeability under ambient conditions. It also permeates (filters) hydrogen (deuterium) isotope ion with high selectivity. These results suggest possible ways of developing novel and efficient hydrogen isotope gas enrichment techniques for manufacturing silicon semiconductors, optical fibers, drug development, nuclear fusion, and other related applications. And yet, despite its importance, experimental studies remain scarce and the separation mechanism contentious. Here, we introduce our recent findings on how quantum tunneling of hydrons through graphene could account for the high hydron selectivity of graphene.

Rotational-energy transfer in H ortho-para conversion on a metal surface; Interplay between electron and phonon systems

Ueta, Hirokazu; Fukutani, Katsuyuki

Journal of Physical Chemistry Letters (Internet), 14(34), p.7591 - 7596, 2023/08

https://doi.org/10.1021/acs.jpclett.3c01209

Step unbunching phenomenon on 4H-SiC (0001) surface during hydrogen etching

Sakakibara, Ryotaro*; Bao, J.*; Yuhara, Keisuke*; Matsuda, Keita*; Terasawa, Tomoo; Kusunoki, Michiko*; Norimatsu, Wataru*

Applied Physics Letters, 123(3), p.031603_1 - 031603_4, 2023/07

https://doi.org/10.1063/5.0153565

We here report a step unbunching phenomenon, which is the inverse of the phenomenon of step bunching. When a 4H-SiC (0001) surface is annealed at a high temperature, step bunching arises due to the different velocities of the step motion in adjacent steps, resulting in steps with a height of more than several nanometers. We found that the bunched steps, thus, obtained by hydrogen etching in an Ar/H atmosphere were "unbunched" into lower height steps when annealed subsequently at lower temperatures. This unbunching phenomenon can be well explained by the consequence of the competition between energetics and kinetics. Our findings provide another approach for the surface smoothing of SiC by hydrogen etching and may give significant insight into the application of SiC power devices and two-dimensional materials growth techniques in general.

Contribution to the carbon neutrality by advanced reactor coexisting with renewable energy system

Ohno, Shuji; Yamano, Hidemasa

Nihon Genshiryoku Gakkai-Shi ATOMO, 65(7), p.438 - 442, 2023/07

https://doi.org/10.3327/jaesjb.65.7_438

This report mainly introduces international/domestic development trends of advanced reactor systems that can coexist with renewable energy in addition to describing the importance of dispatchable energy for the extension of variable renewable energy.