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門井 浩太*; 冠野 裕大*; 青木 聡; 井上 裕滋*
ISIJ International, 64(9), p.1450 - 1456, 2024/07
オーステナイトステンレス鋼の溶接金属中の孔食に及ぼす化学組成の影響について検討した。クロムおよびモリブデンを多く含む試験片は、再活性化率が低いことが示された。チタンの添加は、耐孔食性を著しく低下させた。クロム欠乏領域はM
C
やTiCのような炭化物の近くに形成された。また、凝固時に生成したTiC相がMC析出の核となった。MCの析出により、クロムの拡散による空乏領域が発生し、耐孔食性の劣化を誘発した。
筋田 涼太*; 青木 裕之; 竹中 幹人*; 大内 誠*; 寺島 崇矢*
ACS Macro Letters (Internet), 13(6), p.747 - 753, 2024/06
Herein, we report the water-assisted self-assembly of alternating copolymers bearing imidazolium cations and hydrophobic groups to create water-compatible and nanostructured materials. The copolymers efficiently absorbed water into the cationic segments from the outer environments, depending on the relative humidity. The absorbed water serves as hydrophilic molecules to modulate the weight fraction of hydrophilic/hydrophobic units in the samples. Thus, the morphologies and domain spacing of the nanostructures can be controlled by not only the side chains, but also the amount of absorbed water. The self-assembly of the cationic copolymers, developed herein, afforded universal access to various morphologies, including lamella, gyroid, and cylinder, in addition to the precision control of the domain spacing at the 0.01 nm level.
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
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-Fe
Si
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。
Ikami, Takaya*; 青木 裕之; 寺島 崇矢*
ACS Macro Letters (Internet), 13(4), p.446 - 452, 2024/04
被引用回数：0 パーセンタイル：0.01Microphase separation of random copolymers, as well as that of high 
; low N block copolymers, is promising to construct sub-10-nm structures into materials. Herein, we designed statistical copolymers consisting of 2-hydroxyethyl acrylate (HEA) and N-octadecylacrylamide (ODAAm) to produce crystallization and hydrogen bond-assisted lamellar structure materials. The copolymers not only formed a crystalline lamellar structure with 3-4 nm domain spacing but also maintained an amorphous lamellar structure via phase transition above the melting temperature up to approximately 100 
C. The key is to introduce hydrogen-bonding amide junctions between the octadecyl groups and the polymer backbones, by which the polymer chains are physically fixed at the interface of lamellar structures even above the melting temperature. The stabilization of the lamellar structure by the amide units is also supported by the fact that the lamellar structure of all-acrylate random copolymers bearing hydroxyethyl and crystalline octadecyl groups is disordered above the melting temperature. By spin-coating on a silicon substrate, the HEA/ODAAm copolymer formed a multilayered lamellar thin film consisting of a hydrophilic hydroxyethyl/main chain phase and a hydrophobic octadecyl phase. The structure and order-disorder transition were analyzed by neutron reflectivity.
前田 匡樹*; 田邉 匡生*; 西脇 智哉*; 青木 孝行*; 堂埼 浩二*; 西村 康志郎*; 藤井 翔*; 上野 文義; 田中 章夫*; 鈴木 裕介*; et al.
Transactions of the 27th International Conference on Structural Mechanics in Reactor Technology (SMiRT 27) (Internet), 10 Pages, 2024/03
This study develops assessment methods necessary to obtain a long-term structural integrity outlook for reactor buildings that suffered from the 2011 Great East Japan Earthquake disaster in which access to the site was extremely limited due to high radiation dose rates and high contamination. It is one of the "Nuclear science and technology and human resource development promotion projects" implemented by the Japan Atomic Energy Agency (JAEA) International Collaborative Research Center for Decommissioning and Environment (CLADS) in FY2021 to 2023. This paper introduces an outline and overview of the project.
O/HO vapor generator for contrast-variation neutron scattering有馬 寛*; 高田 慎一; 笠井 聡*; 大内 啓一*; 森川 利明*; 宮田 登*; 宮崎 司*; 青木 裕之; 岩瀬 裕希*; 廣井 孝介; et al.
Journal of Applied Crystallography, 56(6), p.1802 - 1812, 2023/12
被引用回数：0 パーセンタイル：0.02(Chemistry, Multidisciplinary)The contrast-variation technique in neutron scattering experiments plays a pivotal role in distinguishing partial structures within multi-component complexes, facilitating the elucidation of distinct sample constituents. This differentiation is achieved using different isotopes, namely hydrogen and deuterium, which possess varying neutron scattering characteristics. This study presents a novel vapor generator designed for neutron scattering experiments, enabling continuous control of the DO/HO ratio of the vapor. This feature is especially useful for contrast-variation studies. The generator features two saturators and four mass flow controllers, allowing for the rapid and independent generation of DO/HO vapors. Additionally, the incorporation of the two-temperature method ensures accurate dew point control within a margin of 
0.2Cdp. This setup proves useful for conducting time-resolved experiments and can accelerate research on functional polymers, such as polymer electrolyte membranes for fuel cells, where water potential assumes critical importance.
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
被引用回数：0 パーセンタイル：0.00(Polymer Science)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.
青木 裕之
波紋, 33(4), p.142 - 145, 2023/11
In recent years, there has been a strong demand for more advanced adhesion technologies. Neutron reflectometry (NR) is a powerful tool to examine the structure of the adhesion interface because of the large penetration depth to materials and the isotope-dependent contrast mechanism. Examining the effects of absorbed water on epoxy adhesives 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 by NR. The in situ NR measurement revealed the formation of an ~1 nm-thick condensed water layer at the interface with an adherend in a humid atmosphere at a relative humidity of 85%. Water absorbed by epoxy adhesives from a humid atmosphere considerably influences their structure and properties; therefore, the results of NR indicate that the effect of water at the adhesion interface should be considered to develop the adhesion technology. The recent advances in NR overcome the limitation in the applicable field in the conventional NR measurements and would unveil the further information on the fundamental mechanism of the adhesion phenomena.
橋本 慧*; 塩飽 透*; 青木 裕之; 横山 英明*; 眞弓 皓一*; 伊藤 耕三*
Science Advances (Internet), 9(47), p.eadi8505_1 - eadi8505_8, 2023/11
被引用回数：5 パーセンタイル：86.76(Multidisciplinary Sciences)The demand for mechanically robust polymer-based electrolytes is increasing for applications to wearable devices. Young's modulus and breaking energy are essential parameters for describing the mechanical reliability of electrolytes. The former plays a vital role in suppressing the short circuit during charge-discharge, while the latter indicates crack propagation resistance. However, polymer electrolytes with high Young's moduli are generally brittle. In this study, a tough slide-ring solid polymer electrolyte (SR-SPE) breaking through this trade-off between stiffness and toughness is designed on the basis of strain-induced crystallization (SIC) and phase separation. SIC makes the material highly tough (breaking energy, 80 to 100 megajoules per cubic meter). Phase separation in the polymer enhanced stiffness (Young's modulus, 10 to 70 megapascals). The combined effect of phase separation and SIC made SR-SPE tough and stiff, while these mechanisms do not impair ionic conductivity. This SIC strategy could be combined with other toughening mechanisms to design tough polymer gel materials.
金城 克樹*; 藤林 裕己*; 松村 拓輝*; 堀 文哉*; 北川 俊作*; 石田 憲二*; 徳永 陽; 酒井 宏典; 神戸 振作; 仲村 愛*; et al.
Science Advances (Internet), 9(30), p.2736_1 - 2736_6, 2023/07
被引用回数：0 パーセンタイル：0.00(Multidisciplinary Sciences)Superconducting (SC) state has spin and orbital degrees of freedom, and spin-triplet superconductivity shows multiple SC phases because of the presence of these degrees of freedom. However, the observation of spin-direction rotation occurring inside the SC state (SC spin rotation) has hardly been reported. Uranium ditelluride, a recently found topological superconductor, exhibits various SC phases under pressure: SC state at ambient pressure (SC1), high-temperature SC state above 0.5 gigapascal (SC2), and low-temperature SC state above 0.5 gigapascal (SC3). We performed nuclear magnetic resonance (NMR) and ac susceptibility measurements on a single-crystal uranium ditelluride. The b axis spin susceptibility remains unchanged in SC2, unlike in SC1, and decreases below the SC2-SC3 transition with spin modulation. These unique properties in SC3 arise from the coexistence of two SC order parameters. Our NMR results confirm spin-triplet superconductivity with SC spin parallel to b axis in SC2 and unveil the remaining of spin degrees of freedom in SC uranium ditelluride.
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
被引用回数：1 パーセンタイル：40.78(Chemistry, Multidisciplinary)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.
-axis knight shift on UTe with 
= 2.1 K松村 拓輝*; 藤林 裕己*; 金城 克樹*; 北川 俊作*; 石田 憲二*; 徳永 陽; 酒井 宏典; 神戸 振作; 仲村 愛*; 清水 悠晴*; et al.
Journal of the Physical Society of Japan, 92(6), p.063701_1 - 063701_5, 2023/05
被引用回数：8 パーセンタイル：95.84(Physics, Multidisciplinary)Spin susceptibility in the superconducting (SC) state was measured in the higher-quality sample of uranium-based superconductor UTe by using Knight-shift measurements for a magnetic field 
along all three crystalline axes. In the higher-quality sample, the SC transition temperature is about 2.1 K, and the residual electronic term in the specific heat is almost zero. The NMR linewidth becomes narrower and is almost half of that in the previous sample with 
1.6 K when 
and 
. Although the Knight-shift behavior was not so different from the previous results for 
, and , a large reduction in Knight shift along the axis was observed, in contrast with the previous -axis Knight shift result. We discuss the origin of the difference between the previous and present results, and the possible SC state derived from the present results.
Te-NMR on the uranium-based superconductor UTe藤林 裕己*; 金城 克樹*; 仲嶺 元輝*; 北川 俊作*; 石田 憲二*; 徳永 陽; 酒井 宏典; 神戸 振作; 仲村 愛*; 清水 悠晴*; et al.
Journal of the Physical Society of Japan, 92(5), p.053702_1 - 053702_5, 2023/05
被引用回数：2 パーセンタイル：72.40(Physics, Multidisciplinary)To investigate the static and dynamic magnetic properties on the uranium-based superconductor UTe, we measured the NMR Knight shift 
and the nuclear spin lattice relaxation rate 1/
in by Te-NMR on a Te-enriched single-crystal sample. 1/
in is much smaller than 1/ in 
and c, and magnetic fluctuations along each axis are derived from the 1/ measured in parallel to all three crystalline axes. The magnetic fluctuations are almost identical at two Te sites and isotropic at high temperatures, but become anisotropic below 40 K, where heavy-fermion state is formed.
Ni
D
at high 
conditions市東 力*; 鍵 裕之*; 柿澤 翔*; 青木 勝敏*; 小松 一生*; 飯塚 理子*; 阿部 淳*; 齋藤 寛之*; 佐野 亜沙美; 服部 高典
American Mineralogist, 108(4), p.659 - 666, 2023/04
被引用回数：1 パーセンタイル：54.63(Geochemistry & Geophysics)FeNiH(D)の12GPa, 1000Kまでの高温高圧下における相関係と結晶構造をその場X線及び中性子回折測定により明らかにした。今回実験した温度圧力下において、FeNiH(D)ではFeH(D)とは異なり、重水素原子は面心立方構造(fcc)中の四面体サイトを占有しないことが明らかになった。単位重水素あたりの水素誘起膨張体積
は、fcc相で2.45(4) 
、hcp相で3.31(6) であり、FeDにおけるそれぞれの値より著しく大きいことが明らかになった。また、は温度の上昇に伴いわずかに増加した。この結果は、鉄に10%ニッケルを添加するだけで、金属中の水素の挙動が劇的に変化することを示唆している。が圧力に関係なく一定であると仮定すると、地球内核の最大水素含有量は海洋の水素量の1-2倍であると推定される。
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
被引用回数：0 パーセンタイル：0.00(Polymer Science)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.
下北 啓輔*; 山本 勝宏*; 宮田 登*; 中西 洋平*; 柴田 基樹*; 竹中 幹人*; 山田 悟史*; 瀬戸 秀樹*; 青木 裕之; 宮崎 司*
Soft Matter, 19(11), p.2082 - 2089, 2023/03
被引用回数：0 パーセンタイル：0.00(Chemistry, Physical)In the case of poly(methyl methacrylate) (PMMA) thin films on a Si substrate, thermal annealing induces the formation of a layer of PMMA chains tightly adsorbed near the substrate interface, and the strongly adsorbed PMMA remains on the substrate, even after washing with toluene (hereinafter called adsorbed sample). Neutron reflectometry revealed that the concerned structure consists of three layers: an inner layer (tightly bound on the substrate), a middle layer (bulk-like), and an outer layer (surface) in the adsorbed sample. When an adsorbed sample was exposed to toluene vapor, it became clear that, between the solid adsorption layer (which does not swell) and bulk-like swollen layer, there was a "buffer layer" that could sorb more toluene molecules than the bulk-like layer. This buffer layer was found not only in the adsorbed sample but also in the standard spin-cast PMMA thin films on the substrate. When the polymer chains were firmly adsorbed and immobilized on the Si substrate, the freedom of the possible structure right next to the tightly bound layer was reduced, which restricted the relaxation of the conformation of the polymer chain strongly. The "buffer layer" was manifested by the sorption of toluene with different scattering length density contrasts.
induced by magnetic field金城 克樹*; 藤林 裕己*; 北川 俊作*; 石田 憲二*; 徳永 陽; 酒井 宏典; 神戸 振作; 仲村 愛*; 清水 悠晴*; 本間 佳哉*; et al.
Physical Review B, 107(6), p.L060502_1 - L060502_5, 2023/02
被引用回数：9 パーセンタイル：95.72(Materials Science, Multidisciplinary)UTe is a recently discovered spin-triplet superconductor. One of the characteristic features of UTe is a magnetic field ()-boosted superconductivity above 16 T when H is applied exactly parallel to the 
axis. To date, this superconducting (SC) state has not been thoroughly investigated, and the SC properties as well as the spin state of this high- SC (HHSC) phase are not well understood. In this letter, we performed AC magnetic susceptibility and nuclear magnetic resonance measurements and found that, up to 24.8 T, the HHSC state has bulk nature and is quite sensitive to the angle and that its SC character is different from that in the low- SC (LHSC) state. The dominant spin component of the spin-triplet pair is along the axis in the LHSC state but is changed in the HHSC state along the axis. Our results indicate that -induced multiple SC states originate from the remaining spin degrees of freedom.
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
被引用回数：7 パーセンタイル：67.05(Nanoscience & Nanotechnology)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.
下北 啓輔*; 山本 勝宏*; 宮田 登*; 有馬 寛*; 中西 洋平*; 竹中 幹人*; 柴田 基樹*; 山田 悟史*; 瀬戸 秀樹*; 青木 裕之; et al.
Langmuir, 38(41), p.12457 - 12465, 2022/10
被引用回数：0 パーセンタイル：0.00(Chemistry, Multidisciplinary)We measured the neutron reflectivity (NR) of isotactic polypropylene (PP) thin films deposited on Si substrates modified by hexamethyldisilazane (HMDS) at the saturated vapor pressure of deuterated water at 25C and 60C/85% RH to investigate the effect of HMDS on the interfacial water accumulation in PP-based polymer/inorganic filler nanocomposites and metal/resin bonding materials. We found that the amount of water accumulated at the PP/Si interface decreased with increasing immersion time of the Si substrate in a solution of HMDS in hexane prior to PP film deposition. During the immersion of the Si substrate, the HMDS molecules were deposited on the Si substrate as a monolayer without aggregation. Furthermore, the coverage of the HMDS monolayer on the Si substrate increased with increasing immersion time. At 60C and 85% RH, only a slight amount of interfacial water was detected after HMDS treatment for 1200 min. As a result, the maximum concentration of interfacial water was reduced to 0.1 from 0.3, where the latter corresponds to the PP film deposited on the untreated substrate.
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
被引用回数：3 パーセンタイル：34.93(Polymer Science)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.
