Hydrogenation of silicon-bearing hexagonal close-packed iron and its implications for density deficits in the inner core

森 悠一郎*; 鍵 裕之*; 青木 勝敏*; 高野 将大*; 柿澤 翔*; 佐野 亜沙美; 舟越 賢一*

Earth and Planetary Science Letters, 634, p.118673_1 - 118673_8, 2024/05

https://doi.org/10.1016/j.epsl.2024.118673

水素による鉄の体積膨張に対するケイ素の効果を調べるため、高圧高温下でのhcp-FeSiの中性子回折実験とX線回折実験を行った。中性子回折実験は重水素化hcp-FeSiに対して13.5GPa, 900K及び12.1GPa, 300Kで行い、得られたプロファイルからリートベルト解析を用いて水素占有率を決定した。hcp-Fe-SiのP-V-T状態方程式を組み合わせることにより、hcp-FeSiの水素による体積膨張が純粋なhcp鉄の体積膨張よりも10%大きいことを示した。得られた値を用いて、内核の密度欠損を再現できる水素量を見積もったところ、シリコンの影響がない場合に比べて50%減少した。hcp-FeSiで内核の密度欠損を再現した場合、内核と外核で可能な水素量xはそれぞれ0.07と0.12-0.15と計算された。

Microphase separation of cationic homopolymers bearing alkyl ammonium salts into sub-4 nm lamellar materials with water intercalation channels

筋田 涼太*; 今井 彩帆里*; 大内 誠*; 青木 裕之; 寺島 崇矢*

Macromolecules, 56(23), p.9738 - 9749, 2023/12

https://doi.org/10.1021/acs.macromol.3c01722

Constructing ordered ionic nanostructures into bulk polymers and thin films is an important technique to create functional materials, such as polyelectrolytes and proton- and ion-conducting materials, for various applications. Herein, we report microphase separation of cationic homopolymers bearing alkyl ammonium bromides to create sub-4 nm lamellar materials, where an ionic phase is alternatingly layered with a hydrophobic alkyl phase and serves as a channel for water intercalation. We prepared cationic homopolymers with linear or branched alkyl pendants (octyl or 2-ethylhexyl group: C8-eicosyl or 2-octyldodecyl group: C20) via the free radical polymerization of 2-(dimethylamino)ethyl acrylate (DMAEA), followed by the quaternization of the polyDMAEA with corresponding alkyl bromides. The homopolymers carrying linear hexadecyl, octadecyl, and eicosyl groups were crystalline at room temperature, whereas the others were amorphous. The homopolymers bearing linear alkyl pendants longer than the decyl group or branched alkyl pendants larger than the 2-butyloctyl group formed lamellar structures by the self-assembly of the side chains. The domain spacing can be controlled between 2.5 and 3.7 nm by tuning the pendant structures and are smaller than that formed by the corresponding random copolymers. A cationic homopolymer bearing crystalline octadecyl groups maintained lamellar structures up to 210 C far beyond the melting temperature (50 C). The cationic homopolymer further formed a multilayered lamellar thin film on a silicon substrate, in which the cationic layers absorbed water under humid conditions and reversibly released the water therefrom in a N gas atmosphere.

Neutron reflectometry analysis of condensed water layer formation at a solid interface of epoxy resins under high humidity

Liu, Y.*; 宮田 登*; 宮崎 司*; 春藤 淳臣*; 川口 大輔*; 田中 敬二*; 青木 裕之

Langmuir, 39(29), p.10154 - 10162, 2023/06

https://doi.org/10.1021/acs.langmuir.3c01091

Water absorbed by epoxy resins from a humid atmosphere considerably influences their structure and properties. Examining the effects of absorbed water on epoxy resins at their interfaces with solid substrates is crucial because of their adhesive applications in various fields. The spatial distribution of absorbed water in epoxy resin thin films under high humidity was investigated in this study by neutron reflectometry. Water molecules were found to accumulate at the SiO/epoxy resin interface after exposure at a relative humidity of 85% for 8 h. The formation of an ca.1 nm-thick condensed water layer was observed, and the thickness of this layer varied with curing conditions of epoxy systems. Furthermore, the water accumulation at the interface was noted to be affected by high-temperature and high-humidity environments. The formation of the condensed water layer is presumed to be related to the features of the polymer layer near the interface. The construction of the interface layer of epoxy resin would be affected by the interface constraint effect on the cross-linked polymer chain during the curing reaction. This study provides essential information for understanding the factors influencing the accumulation of water at the interface in epoxy resins. In the practical application, the process of improving the construction of epoxy resin near the interface would be a reasonable solution to resist the water accumulation in the interface.

Development of safety design philosophy of HTTR-Heat Application Test Facility

青木 健; 清水 厚志; 野口 弘喜; 倉林 薫; 安田 貴則; 野本 恭信; 飯垣 和彦; 佐藤 博之; 坂場 成昭

Proceedings of 30th International Conference on Nuclear Engineering (ICONE30) (Internet), 9 Pages, 2023/05

本研究では、高温ガス炉と水素製造施設を接続したHTTR(高温工学試験研究炉)-熱利用試験施設に対する安全設計方針を開発した。検討の結果、高圧ガスや可燃性ガスにより想定される災害に対して公衆安全を確保するため、水素製造施設に対しては現行の化学プラントで適用されている法規を適用する安全設計方針を提示した。また、水素製造施設の異常に伴う漏えい可燃性物質の火災爆発や水素製造施設除熱量の変動に対する原子炉施設の通常運転機能の確保等の対策を含め、水素製造施設を接続した原子炉施設特有の安全要件に適合した安全設計方針を提示した。HTTR-熱利用試験施設に対して開発された安全設計方針は、HTTR-熱利用試験施設の基本設計や詳細設計に活用される見込みである。

Development plan for coupling technology between high temperature gas-cooled reactor HTTR and Hydrogen Production Facility, 2; Development plan for coupling equipment between HTTR and Hydrogen Production Facility

水田 直紀; 守田 圭介; 青木 健; 沖田 将一朗; 石井 克典; 倉林 薫; 安田 貴則; 田中 真人; 井坂 和義; 野口 弘喜; et al.

Proceedings of 30th International Conference on Nuclear Engineering (ICONE30) (Internet), 6 Pages, 2023/05

High temperature gas-cooled reactor (HTGR) is expected to extend the use of nuclear heat to a wider spectrum of industrial applications such as hydrogen production, high efficiency power generation, etc., due largely to high temperature heat supply capability as well as inherent safe characteristics. Japan Atomic Energy Agency (JAEA) have been contracted by the Agency for Natural Resources and Energy, part of the Ministry of Economy, Trade and Industry (METI) of Japan, to conduct its Hydrogen Production Demonstration Project Utilizing Very High Temperature. The primary objective of this project is to establish "coupling technology" between HTGR and hydrogen production facility in accordance with "Green Growth Strategy Through Achieving Carbon Neutrality in 2050". From this fiscal year, JAEA initiated a program to produce hydrogen using an HTTR (High Temperature Engineering Test Reactor) to develop coupling technologies between HTGR and hydrogen production facility required for a massive, cost-effective and carbon-free hydrogen production technology. This paper describes the development plan for coupling equipment which is required for an HTTR heat application test as coupling technologies between an HTTR and a hydrogen production facility. The coupling equipment is composed of a high temperature isolation valve to prevent the ingress of the flammable gas and/or the leakage of radioactive materials for nuclear facility, a secondary helium gas circulator to feed a high temperature helium gas, and a high temperature insulation pipe to transport of a high temperature helium gas from an Internal Heat Exchanger (IHX) to a hydrogen production facility. The development plan of coupling equipment contains each target and draft schedule.

Dynamic exchange of amphiphilic random copolymers between micelles in water; Kinetics and mechanism analyzed by TR-SANS

Hibino, Masayuki*; 高田 慎一; 廣井 孝介; 青木 裕之; 寺島 崇矢*

Macromolecules, 56(8), p.2955 - 2964, 2023/04

https://doi.org/10.1021/acs.macromol.2c02408

Amphiphilic random copolymers bearing poly(ethylene glycol) (PEG) and alkyl groups as side chains are intermolecularly self-assembled into size-controlled multichain micelles in water. The random copolymer micelles are known to induce the exchange of their polymer chains, whereas the details of the kinetics and mechanism have not been elucidated yet. Herein, we investigated the exchange kinetics and mechanism of the random copolymer chains between their micelles by time-resolved small-angle neutron scattering (TR-SANS). For this purpose, random copolymers carrying PEG and deuterated butyl or dodecyl groups were designed for deuterated micelles. After mixing deuterated and non-deuterated micelle solutions, the resulting mixtures were monitored by TR-SANS at various concentrations and temperatures. The scattering intensity of the micelle mixtures decayed with time, indicating that deuterated copolymers were gradually mixed with non-deuterated copolymers via chain exchange between their micelles to form micelles consisting of both deuterated and non-deuterated copolymers. The kinetic analysis revealed that the exchange of their polymer chains involved two mechanisms: A unimer release and insertion pathway was dominant in diluted conditions, whereas the contribution of a micelle collision pathway increased with increasing total polymer concentration and temperature. The activation energy of the polymer exchange process was dependent on the hydrophobic alkyl groups and larger than that of a related surfactant micelle.

Interfacial distribution of Nafion ionomer thin films on nitrogen-modified carbon surfaces

吉宗 航*; Kikkawa, Nobuaki*; Yoneyama, Hiroaki*; Takahashi, Naoko*; Minami, Saori*; Akimoto, Yusuke*; Mitsuoka, Takuya*; Kawaura, Hiroyuki*; Harada, Masashi*; 山田 悟史*; et al.

ACS Applied Materials & Interfaces, 14(48), p.53744 - 53754, 2022/11

https://doi.org/10.1021/acsami.2c14574

Chemically modified carbon supports for the cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) show considerable promise for boosting the oxygen reduction reaction. This study evaluated the ionomer distribution of Nafion ionomer thin films on nitrogen (N)-modified carbon surfaces along their depth direction. Neutron reflectivity (NR) measurements performed using the double-contrast technique with HO and DO revealed that the introduction of N functional groups to carbon thin films promoted ionomer adsorption onto the surface under wet conditions (22C, 85% relative humidity). Molecular dynamics (MD) simulations conducted to verify the origin of the robust contact between the ionomer and N-modified carbon surface revealed an ionomer adsorption mechanism on the N-modified carbon surfaces, which involved Coulomb interactions between the positively charged carbon surface and the ionomer side chains with negatively charged sulfonic acid groups. The positive surface charge, which was determined using the contents of the N functional groups estimated by X-ray photoelectron spectroscopy, was found to be sufficient as an impetus for ionomer adsorption. This strategy involving NR measurements and MD simulations can provide insights into the solid-ionomer interfacial structures in a cathode catalyst layer and can therefore be extensively employed in studies on PEFCs.

Water-assisted microphase separation of cationic random copolymers into sub-5 nm lamellar materials and thin films

今井 彩帆里*; 荒川 勝利*; 中西 洋平*; 竹中 幹人*; 青木 裕之; 大内 誠*; 寺島 崇矢*

Macromolecules, 55(20), p.9113 - 9125, 2022/10

https://doi.org/10.1021/acs.macromol.2c01287

Microphase separation of copolymers is a key technique to produce polymer bulk materials or thin films with ordered nanostructures for applications in various research fields including nanotechnologies, electronic devices, among many others. Herein, we report water-assisted microphase separation of amphiphilic random copolymers bearing quaternary ammonium cations and hydrophobic alkyl or oleyl groups in the solid state and the thin films. We investigated the effects of sample preparation protocols and the hydrophobic pendants (a butyl group: C4 - octadecyl or oleyl group: C18), composition, and molecular weight of the copolymers on the microphase separation behavior. By annealing under humid conditions, the copolymers bearing alkyl groups longer than an octyl group (C8) formed sub-5 nm lamellar structures comprising cationic layers and hydrophobic layers. Water hardly remained in the resulting lamellar materials under ambient conditions. The domain spacing was controlled between 3.7 and 5.3 nm by tuning the length of the hydrophobic pendants and composition and was independent of the molecular weight and molecular weight distribution. The cationic random copolymers carrying amorphous hydrophobic pendants provided transparent or translucent polymer materials containing small lamellar structures. The random copolymers further formed multilayered lamellar thin films on silicon substrates by spin-coating the copolymer solutions, followed by a humid annealing process. The layered lamellae were directly observed as terrace structures with about 4-5 nm steps by atomic force microscopy.

HTTR-熱利用試験専門委員会資料集

青木 健; 清水 厚志; 飯垣 和彦; 沖田 将一朗; 長谷川 武史; 水田 直紀; 佐藤 博之; 坂場 成昭

JAEA-Review 2022-016, 193 Pages, 2022/08

JAEA-Review-2022-016.pdf:42.06MB

日本原子力研究開発機構では、高温ガス炉による大量かつ安価なカーボンフリー水素製造技術の実用化を目指し、世界最高の原子炉出口冷却材温度950Cを記録した高温工学試験研究炉(HTTR)を用いて水素製造を行うHTTR-熱利用試験を計画している。HTTR-熱利用試験では、原子力規制委員会からの設置許可取得を通じて、高温ガス炉と水素製造施設の接続に関し、高い安全性を実現する安全設計を確立することが求められている。しかしながら、これまでに原子炉に水素製造施設を接続した例は世界にまだなく、我が国唯一の高温ガス炉であるHTTRを含め、既存の原子力施設を対象とした安全設計ではこのようなシステムを想定していない。そこで、高温ガス炉研究開発センターの下に設置した「HTTR-熱利用試験専門委員会」では、原子力規制委員会による新規制基準への適合性審査に合格したHTTR安全設計をベースに、施設の変更や水素製造施設の接続に伴い安全設計上新たに考慮すべき事象に対する対策を考慮し、HTTR-熱利用試験施設の安全設計案の検討を行った。本稿は、HTTR-熱利用試験専門委員会の技術報告資料や委員コメントとその回答、議事録を取りまとめた。

HTTR-熱利用試験施設の安全設計の考え方

青木 健; 清水 厚志; 飯垣 和彦; 沖田 将一朗; 長谷川 武史; 水田 直紀; 佐藤 博之; 坂場 成昭

JAEA-Technology 2022-011, 60 Pages, 2022/07

JAEA-Technology-2022-011.pdf:2.08MB

日本原子力研究開発機構では、高温ガス炉による大量かつ安価なカーボンフリー水素製造技術の実用化を目指し、世界最高の原子炉出口冷却材温度950Cを達成した高温工学試験研究炉(HTTR)を用いて水素製造を行うHTTR-熱利用試験を計画している。HTTR-熱利用試験では、原子力規制委員会からの設置変更許可取得を通じて、高温ガス炉と水素製造施設の接続に関し、高い安全性を実現する安全設計を確立することが求められている。そこで、HTTR安全設計をベースに、施設の変更や水素製造施設の接続に伴い安全設計上新たに考慮すべき事象に対する対策を考慮し、HTTR-熱利用試験施設の安全設計の考え方を検討した。検討に当たっては、原子炉安全の観点からの十分な安全性を確保することを大前提としつつ、水素製造施設に対して、高圧ガス災害に対する安全確保の多くの実績を有する一般産業法規を適用することを基本方針とした。本報では、水素製造施設への高圧ガス保安法適用に係る合理性や条件、HTTR-熱利用試験施設の安全機能の重要度分類や耐震設計上の重要度分類、重要安全施設の選定、原子炉設置変更許可申請に係る安全設計の考え方に関する検討結果を報告する。