Atomic distribution and local structure in ice VII from in situ neutron diffraction

Yamashita, Keishiro*; Komatsu, Kazuki*; Klotz, S.*; Fabelo, O.*; Fernndez-Daz, M. T.*; Abe, Jun*; Machida, Shinichi*; Hattori, Takanori; Irifune, Tetsuo*; Shimmei, Toru*; et al.

Proceedings of the National Academy of Sciences of the United States of America, 119(40), p.e2208717119_1 - e2208717119_6, 2022/10

https://doi.org/10.1073/pnas.2208717119

Here we present the first elucidation of the disordered structure of ice VII, the dominant high-pressure form of water, at 2.2 GPa and 298 K from both single-crystal and powder neutron diffraction techniques. We reveal the three-dimensional atomic distributions from the maximum entropy method and unexpectedly find a ring-like distribution of hydrogen in contrast to the commonly-accepted discrete sites. In addition, total scattering analysis at 274 K clarified the difference in the intermolecular structure from ice VIII, the ordered counterpart of ice VII, despite an identical molecular geometry. Our complementary structure analyses robustly demonstrate the unique disordered structure of ice VII. Furthermore, these noble findings are related to the proton dynamics which drastically vary with pressure, and will contribute to an understanding of the structural origin of anomalous physical properties of ice VII under pressures.

Summary results of subsidy program for the "Project of Decommissioning and Contaminated Water Management (Development of Analysis and Estimation Technology for Characterization of Fuel Debris (Development of Technologies for Enhanced Analysis Accuracy and Thermal Behavior Estimation of Fuel Debris))"

Koyama, Shinichi; Nakagiri, Toshio; Osaka, Masahiko; Yoshida, Hiroyuki; Kurata, Masaki; Ikeuchi, Hirotomo; Maeda, Koji; Sasaki, Shinji; Onishi, Takashi; Takano, Masahide; et al.

Hairo, Osensui Taisaku jigyo jimukyoku Homu Peji (Internet), 144 Pages, 2021/08

https://dccc-program.jp/3797

JAEA performed the subsidy program for the "Project of Decommissioning and Contaminated Water Management (Development of Analysis and Estimation Technology for Characterization of Fuel Debris (Development of Technologies for Enhanced Analysis Accuracy and Thermal Behavior Estimation of Fuel Debris))" in 2020JFY. This presentation summarized briefly the results of the project, which will be available shortly on the website of Management Office for the Project of Decommissioning and Contaminated Water Management.

Radiation-induced effects on the extraction properties of hexa--octylnitrilo-triacetamide (HONTA) complexes of americium and europium

Toigawa, Tomohiro; Peterman, D. R.*; Meeker, D. S.*; Grimes, T. S.*; Zalupski, P. R.*; Mezyk, S. P.*; Cook, A. R.*; Yamashita, Shinichi*; Kumagai, Yuta; Matsumura, Tatsuro; et al.

Physical Chemistry Chemical Physics, 23(2), p.1343 - 1351, 2021/01

https://doi.org/10.1039/D0CP05720G

The candidate An(III)/Ln(III) separation ligand hexa--octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions using a solvent test loop in conjunction with cobalt-60 gamma irradiation. We demonstrate that HONTA undergoes exponential decay with increasing gamma dose to produce a range of degradation products which have been identified and quantified by HPLC-ESI-MS/MS techniques. The combination of HONTA destruction and degradation product ingrowth, particularly dioctylamine, negatively impacts the extraction and back-extraction of both americium and europium ions. The loss of HONTA was attributed to its reaction with the solvent (-dodecane) radical cation of (HONTA + R) = (7.61 0.82) 10 M s obtained by pulse radiolysis techniques. However, when this ligand is bound to either americium or europium ions, the observed -dodecane radical cation kinetics increase by over an order of magnitude. This large reactivity increase to additional reaction pathways occurring upon metal-ion binding. Lastly nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (100 ns) HONTA radical cation as well as a longer-lived (s) HONTA triplet excited state. These HONTA species are important precursors to the suite of HONTA degradation products observed.

Locally mesh-refined lattice Boltzmann method for fuel debris air cooling analysis on GPU supercomputer

Onodera, Naoyuki; Idomura, Yasuhiro; Uesawa, Shinichiro; Yamashita, Susumu; Yoshida, Hiroyuki

Mechanical Engineering Journal (Internet), 7(3), p.19-00531_1 - 19-00531_10, 2020/06

https://doi.org/10.1299/mej.19-00531

A dry method is one of practical methods for decommissioning the TEPCO's Fukushima Daiichi Nuclear Power Station. Japan Atomic Energy Agency (JAEA) has been evaluating the air cooling performance of the fuel debris by using the JUPITER code based on an incompressible fluid model and the CityLBM code based on the lattice Boltzmann method (LBM). However, these codes were based on a uniform Cartesian grid system, and required large computational time and cost to capture complicated debris structures. We develop an adaptive mesh refinement (AMR) version of the CityLBM code on GPU based supercomputers and apply it to thermal-hydrodynamics problems. The proposed method is validated against free convective heat transfer experiments at JAEA. It is also shown that the AMR based CityLBM code on 4 NVIDIA TESLA V100GPUs gives 6.7x speedup of the time to solution compared with the JUPITER code on 36 Intel Xeon E5-2680v3 CPUs.

Ice I without stacking disorder by evacuating hydrogen from hydrogen hydrate

Komatsu, Kazuki*; Machida, Shinichi*; Noritake, Fumiya*; Hattori, Takanori; Sano, Asami; Yamane, Ryo*; Yamashita, Keishiro*; Kagi, Hiroyuki*

Nature Communications (Internet), 11, p.464_1 - 464_5, 2020/02

https://doi.org/10.1038/s41467-020-14346-5

Water freezes below 0C at ambient pressure ordinarily to ice I, with hexagonal stacking sequence. Under certain conditions, ice with a cubic stacking sequence can also be formed, but ideal ice I without stacking-disorder has never been formed until recently. Here we demonstrate a route to obtain ice I without stacking-disorder by degassing hydrogen from the high-pressure form of hydrogen hydrate, C, which has a host framework isostructural with ice I. The stacking-disorder free ice I is formed from C via an intermediate amorphous or nano-crystalline form under decompression, unlike the direct transformations occurring in ice XVI from neon hydrate, or ice XVII from hydrogen hydrate. The obtained ice I shows remarkable thermal stability, until the phase transition to ice I at 250 K, originating from the lack of dislocations. This discovery of ideal ice I will promote understanding of the role of stacking-disorder on the physical properties of ice as a counter end-member of ice I.

Crystal structure of a high-pressure phase of magnesium chloride hexahydrate determined by X-ray and neutron diffraction methods

Yamashita, Keishiro*; Komatsu, Kazuki*; Hattori, Takanori; Machida, Shinichi*; Kagi, Hiroyuki*

Acta Crystallographica Section C; Structural Chemistry (Internet), 75(12), p.1605 - 1612, 2019/12

https://doi.org/10.1107/S2053229619014670

A crystal structure of a high-pressure phase of magnesium chloride hexahydrate (MgCl 6HO-II) and its deuterated counterpart (MgCl 6DO-II) have been identified for the first time by in-situ single-crystal X-ray and powder neutron diffraction. The crystal structure was analyzed by the Rietveld method for the neutron diffraction pattern based on the initial structure determined by single-crystal X-ray diffraction. This high-pressure phase has a similar framework to that in the known ambient-pressure phase, but exhibits some structural changes with symmetry reduction caused by a subtle modification in the hydrogen-bond network around the Mg(HO) octahedra. These structural features reflect the strain in the high-pressure phases of MgCl hydrates.

Overview of accident-tolerant fuel R&D program in Japan

Yamashita, Shinichiro; Ioka, Ikuo; Nemoto, Yoshiyuki; Kawanishi, Tomohiro; Kurata, Masaki; Kaji, Yoshiyuki; Fukahori, Tokio; Nozawa, Takashi*; Sato, Daiki*; Murakami, Nozomu*; et al.

Proceedings of International Nuclear Fuel Cycle Conference / Light Water Reactor Fuel Performance Conference (Global/Top Fuel 2019) (USB Flash Drive), p.206 - 216, 2019/09

After the nuclear accident at Fukushima Daiichi Power Plant, research and development (R&D) program for establishing technical basis of accident-tolerant fuel (ATF) started from 2015 in Japan. Since then, both experimental and analytical studies necessary for designing a new light water reactor (LWR) core with ATF candidate materials are being conducted within the Japanese ATF R&D Consortium for implementing ATF to the existing LWRs, accompanying with various technological developments required. Until now, we have accumulated experimental data of the candidate materials by out-of-pile tests, developed fuel evaluation codes to apply to the ATF candidate materials, and evaluated fuel behavior simulating operational and accidental conditions by the developed codes. In this paper, the R&D progresses of the ATF candidate materials considered in Japan are reviewed based on the information available such as proceedings of international conference and academic papers, providing an overview of ATF program in Japan.

Free convective heat transfer experiment to validate air-cooling performance analysis of fuel debris

Uesawa, Shinichiro; Yamashita, Susumu; Shibata, Mitsuhiko; Yoshida, Hiroyuki

Proceedings of 11th Korea-Japan Symposium on Nuclear Thermal Hydraulics and Safety (NTHAS-11) (Internet), 6 Pages, 2018/11

Validation of free-convective heat transfer analysis with JUPITER to evaluate air-cooling performance of fuel debris in dry method

Uesawa, Shinichiro; Yamashita, Susumu; Shibata, Mitsuhiko; Yoshida, Hiroyuki

Mechanical Engineering Journal (Internet), 5(4), p.18-00115_1 - 18-00115_13, 2018/08

https://doi.org/10.1299/mej.18-00115

Prediction of chemical effects of Mo and B on the Cs chemisorption onto stainless steel

Di Lemma, F. G.; Yamashita, Shinichiro; Miwa, Shuhei; Nakajima, Kunihisa; Osaka, Masahiko

Energy Procedia, 127, p.29 - 34, 2017/09

https://doi.org/10.1016/j.egypro.2017.08.092

Chemical effects of molybdenum (Mo) and boron (B), which were considered to form compounds with Cs, on the Cs chemisorption were predicted using a chemical equilibrium calculation. It is seen that CsMoO were formed in the chemisorbed compounds. On the other hand, little effects were observed for B. The results suggest that the effects of Mo should be considered for further experimental investigation.