Effects of Cs/Sr intercalation on the structure and electrical conductivity of weathered biotite

Hayakawa, Kosetsu; Muraguchi, Masakazu*; Masebo, Yumeno*; Kojima, Yoichiro*; Oda, Masato*; Yabuta, Rina*; Ishii, Hiroyuki*; Honda, Mitsunori

AIP Advances (Internet), 16(2), p.025337_1 - 025337_8, 2026/02

https://doi.org/10.1063/5.0311080

Weathered biotite (WB), a clay-based layered mineral, becomes thermoelectrically active after molten-salt treatment above 700C. In this study, we investigate how Cs and Sr intercalation influences its local structure and electrical conductivity. WB was treated with molten salts containing CsCl and/or SrCl, and the resulting materials were analyzed using X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray absorption fine structure (XAFS), and four-probe conductivity measurements. XRF verified Cs/Sr incorporation, while XRD confirmed retention of the layered structure. XAFS revealed that, in the Cs/Sr-intercalated sample, the Sr-Si distance shortens by , at elevated temperatures, indicating a closer interaction with the Si-O layer. Electrical conductivity measured from 630860C showed that Cs/Sr-WB exhibits higher conductivity than Sr-WB in the 630780C region. These results suggest that interlayer ion rearrangement enhances conduction pathways, demonstrating the potential of interlayer structural control for designing clay-based thermoelectric materials.

Development of XAFS analysis to elucidate the structural change of weathered biotite under high temperature

Hayakawa, Kosetsu*; Muraguchi, Masakazu*; Masebo, Yumeno*; Kojima, Yoichiro*; Oda, Masato*; Yabuta, Rina*; Ishii, Hiroyuki*; Honda, Mitsunori

e-Journal of Surface Science and Nanotechnology (Internet), 23(3), p.290 - 295, 2025/07

https://doi.org/10.1380/ejssnt.2025-041

We are developing materials using clay minerals for thermoelectric materials that can be used at high temperatures in environmental friendly applications. We have succeeded in obtaining thermoelectric properties at high temperatures, but we do not know why these properties are exhibited. In order to elucidate the structural changes of weathered biotite under high temperature conditions, we will develop an XAFS analysis method and clarify the local structure of Fe at high temperatures. The local structure analysis of Fe in samples sintered in atmospheric and vacuum environments reveals changes in the chemical bonding state of Fe.

Desorption of cesium from Fukushima soils using a mechanochemical method

Kaneta, Yui; Kobayashi, Toru; Tsuji, Takuya; Honda, Mitsunori; Yokoyama, Keiichi; Mampuku, Yuzo*; Yaita, Tsuyoshi*

Clays and Clay Minerals, 73, p.e26_1 - e26_8, 2025/04

https://doi.org/10.1017/cmn.2025.9

The desorption behavior of stable Cs adsorbed onto weathered biotite (WB), a clay mineral abundant in Fukushima soils, was investigated using a mechanochemical (MC) method that combines physical grinding by ball impact with a wet process promoting chemical reactions. The results, oxalic acid desorbed Cs to some extent without significantly affecting the layered structure of the clay minerals; ammonium chloride, showed an exfoliation of the layer structure, resulting in a stable desorption of Cs independent of samples. Regarding the real soil samples collected in Fukushima, the MC method using ammonium chloride solution desorbed 80% of Cs. In contrast, oxalic acid did not always result in radioactive Cs made sufficiently desorbed for all the samples. Based on these findings, the MC method with ammonium chloride effectively promotes radioactive Cs desorption from interlayers due to synergistic effects from the layered structure's exfoliation and chemical interaction.

EXAFS investigation of strontium adsorption onto weathered biotite

Honda, Mitsunori; Kaneta, Yui; Yaita, Tsuyoshi

AIP Advances (Internet), 13(1), p.015314_1 - 015314_6, 2023/01

https://doi.org/10.1063/5.0106879

The efficiency of the sorption of Sr on weathered biotite, a type of clay minerals was investigated. Removal of Sr and Cs is important in the treatment of contaminated water from the 1F accident, which is one of the radionuclide waste treatment problems. We focused on developing an adsorption method for Sr ions using weathered biotite, which are abundant in Fukushima. Applying a molten salt treatment, the amount of sorbed Sr simply increased as the added mass ratio of strontium chloride (SrCl) increased from 1:1, 1:5, and 1:10 for the one-fold, five-fold, and ten-fold additions of SrCl, respectively. Then, the crystal structure of weathered biotite as an adsorbent was evaluated by X-ray diffraction (XRD) analysis. Thus, it was observed that the WB retained its original crystal structure even after the sorption of Sr. Extended X-ray absorption fine structure (EXAFS) analysis was performed to investigate the local sorption structure of Sr in the WB. The results revealed that Sr was preferentially sorbed into the SiO and AlO layers when Sr was in the low mass ratio, while, it was mainly sorbed into the SiO layer when the ratio was high.

Marking actinides for separation; Resonance-enhanced multiphoton charge transfer in actinide complexes

Matsuda, Shohei; Yokoyama, Keiichi; Yaita, Tsuyoshi; Kobayashi, Toru; Kaneta, Yui; Simonnet, M.; Sekiguchi, Tetsuhiro; Honda, Mitsunori; Shimojo, Kojiro; Doi, Reisuke; et al.

Science Advances (Internet), 8(20), p.eabn1991_1 - eabn1991_11, 2022/05

https://doi.org/10.1126/sciadv.abn1991

no abstracts in English

Synchrotron X-ray standing wave Characterization of atomic arrangement at interface between transferred graphene and -AlO(0001)

Entani, Shiro*; Honda, Mitsunori; Naramoto, Hiroshi*; Li, S.*; Sakai, Seiji*

Surface Science, 704, p.121749_1 - 121749_6, 2021/02

https://doi.org/10.1016/j.susc.2020.121749

Graphene is expected to be one of the most promising materials for nanoelectronics and spintronics. In most graphene-based devices, the graphene channel is placed on insulating substrates. Therefore, the study of inter-facial interactions between graphene and the insulator surface is of critical importance. In this study, the vertical arrangement of graphene which is transferred on -AlO(0001) has been studied by normal incidence X-ray standing wave (NIXSW) technique. The analysis of the NIXSW profile reveals that the graphene layer is located at 3.57 () above the -AlO(0001) surface, which is larger than the interlayer distance of graphite at 3.356 (). Micro- Raman spectroscopy shows that the transferred graphene has a limited spatial distribution of hole concentration. The present study shows that transferred graphene on the sapphire substrate followed by vacuum-annealing has an atomically flat surface free from residual contaminations such as organic compounds and there occurs the hole-doping in graphene.

Effective adsorption and collection of cesium from aqueous solution using graphene oxide grown on porous alumina

Entani, Shiro*; Honda, Mitsunori; Shimoyama, Iwao; Li, S.*; Naramoto, Hiroshi*; Yaita, Tsuyoshi; Sakai, Seiji*

Japanese Journal of Applied Physics, 57(4S), p.04FP04_1 - 04FP04_4, 2018/04

https://doi.org/10.7567/JJAP.57.04FP04

Proposed cesium-free mineralization method for soil decontamination; Demonstration of cesium removal from weathered biotite

Honda, Mitsunori; Shimoyama, Iwao; Kogure, Toshihiro*; Baba, Yuji; Suzuki, Shinichi; Yaita, Tsuyoshi

ACS Omega (Internet), 2(12), p.8678 - 8681, 2017/12

https://doi.org/10.1021/acsomega.7b01304

Development of cesium-free mineralization for decontamination and reuse of radioactive contaminated soil in Fukushima

Shimoyama, Iwao; Honda, Mitsunori; Kogure, Toshihiro*; Baba, Yuji; Hirao, Norie*; Okamoto, Yoshihiro; Yaita, Tsuyoshi; Suzuki, Shinichi

Photon Factory News, 35(1), p.17 - 22, 2017/05

http://pfwww.kek.jp/publications/pfnews/35_1/saikin2.pdf

We introduce Cs-free mineralization (CFM) for Cs removal and reuse of radioactive-contaminated soil in Fukushima and report recent work conducted in the BL27A beamline in Photon Factory. In this work, we investigated compositional and structural changes of Cs-sorbed weathered biotite (WB) before and after heating treatment with addition of NaCl-CaCl salts under low-pressure condition, to study Cs desorption mechanism from clay minerals. X-ray fluorescence spectroscopy clarified that almost all Cs and K were removed with the salts at 700 C. On the other hand, Ca increased with heating temperature. X-ray diffraction and transmission electron microscopy analysis clarified that phase transitions from WB to some Ca-rich silicate minerals, e.g., augite, were caused by the heating treatment with the salt. Based on these results, CFM is proposed for Cs removal utilizing the mechanism in which large monovalent cations are discharged with accompanying the phase transition. We also discuss the role of Cl in this reaction showing chemical bonding change of Cl observed using X-ray absorption spectroscopy in the early stage of the chemical reaction.

X-ray absorption fine structure at the cesium 3 absorption edge for cesium sorbed in clay minerals

Honda, Mitsunori; Shimoyama, Iwao; Okamoto, Yoshihiro; Baba, Yuji; Suzuki, Shinichi; Yaita, Tsuyoshi

Journal of Physical Chemistry C, 120(10), p.5534 - 5538, 2016/03

https://doi.org/10.1021/acs.jpcc.5b12378