Fluorous and organic extraction systems; A Comparison from the perspectives of coordination structures, interfaces, and bulk extraction phases

Ueda, Yuki; Micheau, C.; Akutsu, Kazuhiro*; Tokunaga, Kohei; Yamada, Masako*; Yamada, Norifumi*; Bourgeois, D.*; Motokawa, Ryuhei

Langmuir, 40(46), p.24257 - 24271, 2024/11

https://doi.org/10.1021/acs.langmuir.4c02268

Microscopic structures in liquid-liquid extraction, such as structuration between extractants or extracted complexes in bulk organic phases and at interfaces, can influence macroscopic phenomena, such as the distribution behavior of solutes, including extraction efficiency, selectivity, and phase separation of the organic phase. In this study, we correlated the macroscopic behavior of the extraction of Zr(IV) ions from nitric acid solutions with microscopic structural information in order to understand at the molecular level the key factors contributing to the higher metal ion extraction performance in the fluorous extraction system comprising fluorous phosphate (TFP) in perfluorohexane as compared to the analogous organic extraction system comprising organic phosphate (THP) in n-hexane. Extended X-ray absorption fine structure, neutron reflectometry, and small-angle neutron scattering revealed the local coordination structure around the Zr(IV) ion, the accumulation of extractant molecules at the interface, and the structuration of extractant molecules in the bulk extraction phase, respectively. In the fluorous extraction system, extractant aggregates with were formed after contact with nitric acid. In contrast, in the organic extraction system, only extractant dimers were formed. We speculate that differences in the local coordination structure around the Zr(IV) ion and the structuration of the extractant molecules in the bulk extraction phase contribute to the high Zr(IV) extraction performance in the fluorous extraction system. In particular, the size of the aggregates hardly changed with increasing Zr(IV) concentration in the fluorous phase, which may be closely related to the absence of phase splitting in the fluorous extraction system.

Interpenetration of rubber and silane coupling agent on an inorganic substrate revealed by spin-contrast-variation neutron reflectivity

Kumada, Takayuki; Iwahara, Daisuke*; Nishitsuji, Shotaro*; Akutsu, Kazuhiro*; Miura, Daisuke; Motokawa, Ryuhei; Sugita, Tsuyoshi; Torikai, Naoya*; Amino, Naoya*; Oku, Takayuki; et al.

Journal of Physical Chemistry C, 128(21), p.8797 - 8802, 2024/05

https://doi.org/10.1021/acs.jpcc.4c00963

We elucidated the entanglement of polybutadiene and silane coupling agent (SCA) molecules bound to Si substrates using spin-contrast-variation (SCV) neutron reflectivity (NR). In an annealed integral blend film of polybutadiene and SCA, a SCA layer generated on the Si substrate was composed of 70 vol. percent SCA molecules extended perpendicularly from the silicon substrate and entangled with 30 vol. percent polybutadiene molecules. By contrast, in an SCA-precoated polybutadiene film, the SCA-precoated layer is composed of densely packed SCA molecules forming crystal-like structure, and thus did not become entangled with the postcoated polybutadiene molecules. This poor entanglement resulted in poor binding between polybutadiene and Si substrate.

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

Liu, Y.*; Miyata, Noboru*; Miyazaki, Tsukasa*; Shundo, Atsuomi*; Kawaguchi, Daisuke*; Tanaka, Keiji*; Aoki, Hiroyuki

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

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

Structure analysis of a buried interface between organic and porous inorganic layers using spin-contrast-variation neutron reflectivity

Kumada, Takayuki; Miura, Daisuke*; Akutsu, Kazuhiro*; Oishi, Kazuki*; Morikawa, Toshiaki*; Kawamura, Yukihiko*; Suzuki, Junichi*; Oku, Takayuki; Torikai, Naoya*; Niizeki, Tomotake*

Journal of Applied Crystallography, 55(5), p.1147 - 1153, 2022/10

AA2021-0903.pdf:1.06MB

https://doi.org/10.1107/S1600576722007506

Spin-contrast-variation neutron reflectivity obtains multiple reflectivity curves from a single sample and a single beam source. We used the strong point of the technique to reveal that, although methylated-perhydropolysilazane-derived silica layer has a higher porosity near the interface with acrylic urethane resin, the resin did not permeate the pore network.

New design of a sample cell for neutron reflectometry in liquid-liquid systems and its application for studying structures at air-liquid and liquid-liquid interfaces

Akutsu-Suyama, Kazuhiro*; Yamada, Norifumi*; Ueda, Yuki; Motokawa, Ryuhei; Narita, Hirokazu*

Applied Sciences (Internet), 12(3), p.1215_1 - 1215_10, 2022/02

https://doi.org/10.3390/app12031215

no abstracts in English

SUIREN (polarized neutron reflectometer)

Takeda, Masayasu

Hamon, 31(1), p.18 - 19, 2021/02

https://doi.org/10.5611/hamon.31.1_18

no abstracts in English

New progress in the observation and application of the laser-plasma in the semiconductors and dielectrics, 2; Study of non-thermal effects on femtosecond laser ablation of transparent dielectrics through the measurements of spallation dynamics

Kumada, Takayuki

Purazuma, Kaku Yugo Gakkai-Shi, 96(4), p.176 - 180, 2020/04

AA2019-0379.pdf:0.66MB

We have developed time-resolved reflectivity measurement system using femtosecond laser pulses, which can measure structure of thin films generated by non-thermal effect.

Development of dynamic nuclear polarization system for spin-contrast-variation neutron reflectometry

Kumada, Takayuki; 7 of others*

JPS Conference Proceedings (Internet), 22, p.011015_1 - 011015_5, 2018/11

https://doi.org/10.7566/JPSCP.22.011015

Neutron reflectometers in J-PARC

Yamada, Norifumi*; Takeda, Masayasu; Yamazaki, Dai

Hamon, 24(4), p.288 - 295, 2014/11

https://doi.org/10.5611/hamon.24.4_288

no abstracts in English

Development of multilayer mirrors for use in the wavelength region of 4 nm

Ishino, Masahiko; Yoda, Osamu*; Koike, Masato

JAERI-Research 2005-019, 13 Pages, 2005/09

JAERI-Research-2005-019.pdf:1.46MB

We have developed soft X-ray multilayer mirrors for use around the wavelength region of 4 nm including the K-absorption edge of carbon (). We have chosen CoO and Cr as the final candidate materials for absorber layers, and SiO and Sc for the spacer materials as the result of theoretical invitation. CoO/SiO, CoO/Sc and Cr/Sc multilayer mirrors have been fabricated by means of an ion beam sputtering (IBS) method. As the result of structure evaluations with X-ray diffraction measurement, we have found that the fabricated CoO/Sc and Cr/Sc multilayer mirrors have stable structures. Soft X-ray reflectivity measurements for fabricated multilayer mirrors are carried out in the wavelength region of 4 nm with a synchrotron radiation source. We have found that the Cr/Sc multilayer mirror has a high soft X-ray reflectivity. However, soft X-ray reflectivities below the absorption edge of carbon are reduced. The analyses obtained by EPMA and SIMS suggested that this phenomenon was attributed to contamination of carbon.