Development of a DO/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

https://doi.org/10.1107/S1600576723009780

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.

Direct observation of concentration fluctuations in Au-Si eutectic liquid by small-angle neutron scattering

坂口 佳史*; 高田 慎一; 川北 至信; 藤村 由希; 近藤 啓悦

Journal of Physics; Condensed Matter, 35(41), p.415403_1 - 415403_11, 2023/10

https://doi.org/10.1088/1361-648X/ace577

It is well-known that eutectic gold-silicon (Au-Si) alloys exhibit anomalous melting point depression, which is more than 1000 C from the melting point of elemental Si (1414 C). The melting point depression in eutectic alloys is generally explained in terms of a decrease of the free energy by mixing. However, it is difficult to understand the anomalous melting point depression only from the stability of the homogeneous mixing. Some researchers suggest that there are concentration fluctuations in the liquids, where the atoms are inhomogeneously mixed. In this paper, we measure the small-angle neutron scattering (SANS) of AuSi (eutectic composition) and AuSi (off-eutectic composition) at temperatures from room temperature to 900 C in both solid and liquid states to observe such concentration fluctuations directly.

Development of spin-contrast-variation neutron powder diffractometry for extracting the structure factor of hydrogen atoms

三浦 大輔*; 熊田 高之; 関根 由莉奈; 奥 隆之; 高田 慎一; 廣井 孝介; 岩田 高広*

J-PARC 22-02; J-PARC MLF Annual Report 2021, p.6 - 7, 2022/03

https://mlfinfo.jp/_src/resource/PEPngy9XwF/MLF_AR2021.pdf

スピンコントラスト変調中性子粉末結晶構造解析法を用いてグルタミン酸結晶を測定したところ、水素核偏極度に応じて偏極中性子の回折ピーク強度がピークごとに大きく変化した。その変化を解析することにより水素原子間同士の相関関数および水素原子と他の原子との相関関数を抽出することに成功した。

Spontaneous formations of nanoconfined water in ionic liquids by small-angle neutron scattering

阿部 洋*; 根本 文也*; 廣井 孝介; 大石 一城*; 高田 慎一

Journal of Molecular Liquids, 346, p.117035_1 - 117035_6, 2022/01

https://doi.org/10.1016/j.molliq.2021.117035

In this study, monodispersive nanoconfined water ("water pocket") is organized spontaneously in hydrophilic ionic liquid (IL). The IL is 1-alkyl-3-methylimidazolium nitrate ([Cmim][NO] = 2, 6, and 8). By small-angle neutron scattering (SANS), DO aggregations in the IL are detected. There are no SANS peaks for [Cmim][NO]-DO, but, in [Cmim][NO]- mol% DO, a SANS peak can be observed at mol%. The peak intensity, position, and profile change according to water concentration and temperature. Pure [Cmim][NO] has a distinct SANS peak, reflecting on the nanodomains at room temperature. Above 70 mol%, the SANS peak of [Cmim][NO]-DO sharply increases and shifts to the low-Q position. The water pocket develops proportionate to water concentration, and its morphologies are visualized using an bead model. The alkyl chain length dependence of the water pocket is clarified by a three-dimensional reconstruction method.

Dynamics of water in a catalyst layer of a fuel cell by quasielastic neutron scattering

伊藤 華苗; 山田 武*; 篠原 朗大*; 高田 慎一; 川北 至信

Journal of Physical Chemistry C, 125(39), p.21645 - 21652, 2021/10

https://doi.org/10.1021/acs.jpcc.1c06014

The catalyst layer (CL) in polymer electrolyte fuel cells (PEFCs) plays a critical role in the performance of a PEFC. In this study, we investigate the water dynamics in the CL using quasielastic neutron scattering (QENS) and small-angle neutron scattering. The temperature dependence of the mean square displacement u shows that the freezing of water does not occur at a melting temperature in the Nafion thin film of the CL, suggesting that the water is confined in a smaller region than 15 . The QENS measurements established three kinds of water in the CL: immobile water tightly connected to a sulfonic group, water in a fast mode assigned to free diffusion restricted in a sphere, and water in a slow mode described by a jump diffusion model. Assuming that these three modes were independent, the number of water molecules in each mode was estimated. On discussing the structure and dynamics elucidated in the study, we finally conclude that the coupled model of the fast and slow modes is plausible for describing the diffusion of water confined in the thin Nafion film of the CL.

Distinguishing adsorbed and deposited ionomers in the catalyst layer of polymer electrolyte fuel cells using contrast-variation small-angle neutron scattering

原田 雅史*; 高田 慎一; 岩瀬 裕希*; 梶谷 修司*; 門浦 弘明*; 金谷 利治*

ACS Omega (Internet), 6(23), p.15257 - 15263, 2021/06

https://doi.org/10.1021/acsomega.1c01535

The ionomers distributed on carbon particles in the catalyst layer of polymer electrolyte fuel cells (PEFCs) govern electrical power via proton transport and oxygen permeation to active platinum. Thus, ionomer distribution is a key, to PEFC performance. This distribution is characterized by ionomer adsorption and deposition onto carbon during the catalyst-ink coating process; however, the adsorbed and deposited ionomers cannot easily be distinguished in the catalyst layer. Therefore, we identified these two types of ionomers based on the positional correlation between the ionomer and carbon Particles. From fitting with a model for a fractal aggregate of polydisperse core-shell spheres we determined the adsorbed-ionomer thickness on the carbon particle to be 51 angstrom land the deposited-ionomer amount for the total ionomer to be 50%. Our technique for ionomer differentiation can be used to optimally design PEFC catalyst layers.

Development of spin-contrast-variation neutron powder diffractometry for extracting the structure factor of hydrogen atoms

三浦 大輔*; 熊田 高之; 関根 由莉奈; 元川 竜平; 中川 洋; 大場 洋次郎; 大原 高志; 高田 慎一; 廣井 孝介; 森川 利明*; et al.

Journal of Applied Crystallography, 54(2), p.454 - 460, 2021/04

AA2020-0724.pdf:2.05MB

https://doi.org/10.1107/S1600576721000303

山形大学が原子核物理実験用に開発した結晶試料の核スピン偏極技術を、スピンコントラスト偏極中性子回折測定法に展開し、水素核偏極化されたグルタミン酸を用いて粉末結晶試料中の水素の配向および凝集・分散などの構造情報を抽出できることを実証した。

NACore amyloid formation in the presence of phospholipids

Pallbo, J.*; 今井 正幸*; Gentile, L.*; 高田 慎一; Olsson, U.*; Sparr, E.*

Frontiers in Physiology (Internet), 11, p.592117_1 - 592117_13, 2020/12

https://doi.org/10.3389/fphys.2020.592117

In this paper we investigate interactions between an aggregating peptide and phospholipid membranes, focusing on the nanometer-scale structures of the aggregates formed, as well as on the effect on the aggregation process. As a model system, we use the small amyloid-forming peptide named NACore, which is a fragment of the central region of the protein alpha-synuclein that is associated with Parkinson's disease. We find that phospholipid vesicles readily associate with the amyloid fibril network in the form of highly distorted and trapped vesicles that also may wet the surface of the fibrils.

Structural investigation of sulfonated polyphenylene ionomers for the design of better performing proton-conductive membranes

椎野 佳祐*; 大友 季哉; 山田 武*; 有馬 寛*; 廣井 孝介; 高田 慎一; 三宅 純平*; 宮武 健治*

ACS Applied Polymer Materials (Internet), 2(12), p.5558 - 5565, 2020/11

https://doi.org/10.1021/acsapm.0c00895

To achieve high-performance proton-exchange membranes (PEMs), understanding of the polymer structure/ property relationship is crucial. In particular, the structure of water clusters (number, size, interdomain distance, interconnectivity, etc.) and hydrophobic domains dominates important membrane properties, such as proton conductivity and mechanical strength, which can be adjusted by the monomer sequence in the polymer chains. In the present paper, we have prepared three sulfonated polyphenylene-based copolymers (SPP-MP, SPP-BP, and SPP-QP) whose main chain components were the same but their sequence differed by the use of different hydrophobic monomers (monophenylene, -MP; biphenylene, -BP; and quinquephenylene, -QP, respectively). Careful investigation of the proton nuclear magnetic resonance (1H NMR) spectra suggested that the randomness of the hydrophilic component (sulfophenylene unit) was dominated by the hydrophobic component: 51 % for -MP, 32 % for -BP, and 19 % for -QP, respectively. Transmission electron microscopy (TEM) observation of the three polyphenylene ionomer membranes revealed that the lower randomness of the hydrophilic component caused a larger hydrophilic domain size in their phase-separated morphology under dry conditions. Small-angle X-ray scattering (SAXS) measurements suggested that SPP-QP, with the lowest randomness of the hydrophilic component, possessed the most pronounced periodic structure under humidified conditions.

Nanostructures and viscosities of nafion dispersions in water/ethanol from dilute to concentrated regimes

Gupit, C. I.*; Li, X.*; Maekawa, Ryosuke*; Hasegawa, Naoki*; 岩瀬 裕希*; 高田 慎一; 柴山 充弘*

Macromolecules, 53(4), p.1464 - 1473, 2020/02

https://doi.org/10.1021/acs.macromol.9b02314

The present work involved a systematic analysis of both the structural and rheological properties of Nafion dispersions carefully prepared using a standard procedure, ranging from dilute (0.1 wt %) to highly concentrated (30 wt %) conditions. Small-angle X-ray scattering confirmed the cylindrical structure of Nafion in dispersion and the unique interactions of Nafion particles acting as polyelectrolytes. Three different scaling relationships involving the zero-shear viscosities of the Nafion dispersions were determined for specific concentration regimes. However, at the upper concentration limit of approximately 30 wt %, the viscosity greatly deviated from these scaling relationships and significant shear thinning was observed. Simultaneous analyses using rheology and small-angle neutron scattering determined fully isotropic spatial correlations on a length scale of less than 60 nm, even when high shear was applied.