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.

Structure analysis of asymmetric interface using spin-contrast-variation neutron reflectometry

Kumada, Takayuki; Miura, Daisuke*; Akutsu, Kazuhiro*; Oku, Takayuki; Torikai, Naoya*; Niizeki, Tomotake*

Hamon, 32(4), p.165 - 168, 2022/11

https://doi.org/10.5611/hamon.32.4_165

We demonstrated the advantage of spin-contrast-variation neutron reflectometry on the structure analysis of buried interface between resin and porous silica layers. The interface structure was not reproduced by the normal Gaussian model, but by the asymmetric interface model where crosslinked polymer chains neither permeate the pore nor follow the surface roughness of the silica layer.

Improved performance of wide bandwidth neutron-spin polarizer due to ferromagnetic interlayer exchange coupling

Maruyama, Ryuji; Yamazaki, Dai; Aoki, Hiroyuki; Akutsu, Kazuhiro*; Hanashima, Takayasu*; Miyata, Noboru*; Soyama, Kazuhiko; Bigault, T.*; Saerbeck, T.*; Courtois, P.*

Journal of Applied Physics, 130(8), p.083904_1 - 083904_10, 2021/08

https://doi.org/10.1063/5.0062072

Improvement in sputtering rate uniformity over large deposition area of large-scale ion beam sputtering system

Maruyama, Ryuji; Yamazaki, Dai; Akutsu, Kazuhiro*; Hanashima, Takayasu*; Miyata, Noboru*; Aoki, Hiroyuki; Soyama, Kazuhiko

JPS Conference Proceedings (Internet), 33, p.011092_1 - 011092_6, 2021/03

https://doi.org/10.7566/JPSCP.33.011092

no abstracts in English

Development of spin-contrast-variation neutron reflectometry for structural analyses of multilayer films

Kumada, Takayuki; Miura, Daisuke*; Akutsu, Kazuhiro*; Suzuki, Junichi*; Torikai, Naoya*

Hamon, 30(4), p.207 - 211, 2020/11

https://doi.org/10.5611/hamon.30.4_207

We developed a technique of spin-contrast-variation neutron reflectivity (SCV-NR) for structural analyses of multilayer films. The SCV-NR curves of the polystyrene monolayer film were precisely reproduced using a common set of structural parameters and neutron scattering length density at each proton polarization. This result ensures that SCV-NR curves are not deformed by inhomogeneous PH due to the spin-diffusion mechanism. The number of structural parameters of the lamellar microphase-separated poly(styrene-block-isoprene) thin film is too large to determine with a single unpolarized reflectivity curve only. However, these parameters converged through the global analysis of the SCV-NR curves. In this manner, SCV-NR determines the structure of multilayer films while excluding the incorrect structural model that accidentally accounts for a single unpolarized reflectivity curve only.

Development of spin-contrast-variation neutron reflectometry for the structural analysis of multilayer films

Kumada, Takayuki; Akutsu, Kazuhiro*; Oishi, Kazuki*; Morikawa, Toshiaki*; Kawamura, Yukihiko*; Sahara, Masae*; Suzuki, Junichi*; Torikai, Naoya*

Journal of Applied Crystallography, 52(5), p.1054 - 1060, 2019/10

AA2018-0116.pdf:0.86MB

https://doi.org/10.1107/S1600576719010616

We developed a technique of spin-contrast-variation neutron reflectometry (SCV-NR). Polarized-neutron reflectivity curves of film samples vary as a function of their proton-polarization P. The P-dependent reflectivity curves of a polystyrene film was precisely reproduced using a common set of structure parameters and the P-dependent neutron scattering length. The reflectivity curve of poly (styrene-block-isoprene) (PSPI) presented a shoulder attributed to holes with the depth corresponding to one period of periodic lamellae on the free surface only at a specific P. In this way, structural information about specific surfaces or interfaces can be obtained by controlling the P.

Complexation properties and structural character of lanthanides complexes of -hetero donor ligand BIZA

Kobayashi, Toru; Akutsu, Kazuhiro*; Nakase, Masahiko*; Suzuki, Shinichi; Shiwaku, Hideaki; Yaita, Tsuyoshi

Separation Science and Technology, 54(13), p.2077 - 2083, 2019/02

https://doi.org/10.1080/01496395.2019.1575880

Development of separation reagent, which can efficiently separate lanthanides, is of increasing importance because it concerns establishment of purification and recycle techniques rare-earth elements. In our research group, several hetero donor type ligands, which have both oxygen and heterocyclic nitrogen atoms as donor atoms, were developed and revealed that this type of ligands show the selective complexation with specific lanthanide. In this paper, we will discuss the lanthaides complexation properties of the hetero donor type ligand containing benzimidazole group as nitrogen donor (-methyl--phenyl-2-(1-benzimidazol-2-yl)-pyridine-6-carboxamide) based on structural investigation by crystallography.

Deuterated Materials Enhancing Neutron Science for Structure Function Applications; October 19th-20th, 2017, Ibaraki Quantum Beam Research Center

Akutsu, Kazuhiro*; Adachi, Motoyasu*; Kawakita, Yukinobu

JAEA-Review 2018-002, 36 Pages, 2018/03

JAEA-Review-2018-002.pdf:4.67MB

Since J-PARC started operation for user programs with high-intensity pulsed neutron beams, many material and life science studies have been carried out at J-PARC. Since partial or complete deuteration of organic compounds for contrast variation in the scattering length densities of materials is one of the most effective techniques in the application of neutron scattering analysis, deuterated materials have led to significant progress in our understanding of the structure of novel organic materials. Aiming at accelerating development of deuteration activities in our country, an international workshop "Deuterated Materials Enhancing Neutron Science for Structure Function Applications" was held as a J-PARC Workshop at Ibaraki Quantum Beam Research Center from 19th October to 20th October in 2017. In this workshop, the chemical/biological deuteration activities and recent scientific results of deuterated materials enhancing neutron study in Japan and other countries were discussed by domestic/foreign deuteration and neutron scientists. This is a report of the workshop summarized by organizers.

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

Motokawa, Ryuhei; Kobayashi, Toru; Endo, Hitoshi*; Ikeda, Takashi; Yaita, Tsuyoshi; Suzuki, Shinichi; Narita, Hirokazu*; Akutsu, Kazuhiro*; Heller, W. T.*

Journal of Nuclear Science and Technology, 53(8), p.1205 - 1211, 2016/08

https://doi.org/10.1080/00223131.2015.1102100