Ion-pairing extraction and their reaction modeling of anionic M-Cl species with cationic NTAamide(C6) extractant and comparison with density functional theory calculations

Kinoshita, Ryoma; Sasaki, Yuji; Kaneko, Masashi; Matsumiya, Masahiko*; Shinoku, Kota*; Shiroishi, Hidenobu*

Hydrometallurgy, 222, p.106159_1 - 106159_12, 2023/10

https://doi.org/10.1016/j.hydromet.2023.106159

Solvent extraction is conducted using a total of 20 metals revealing high stability constants with Cl and hexahexyl-nitrilotriacetamide (NTAamide(C6)) extractant. The metals used here may behave as anions at high Cl concentrations, and NTAamide(C6), which contains a tertiary N atom, is protonated under acidic conditions. Most of the metal ions in this study display higher distribution ratios (D(M)) from HCl than those from HNO, and exhibit 1:1 stoichiometries with NTAamide. Following the experimental results, the association constants and distribution coefficients of the group 12 elements are calculated via ion-pair extraction modeling using density functional theory calculations, and the simulations of D yield calculated values with the same trend as that of the measured values.

Solidification and stabilization of strontium and chloride ions in thermally treated calcium aluminate cement modified with or without sodium polyphosphate

Irisawa, Keita; Namiki, Masahiro*; Taniguchi, Takumi; Garcia-Lodeiro, I.*; Kinoshita, Hajime*

Cement and Concrete Research, 156, p.106758_1 - 106758_8, 2022/06

https://doi.org/10.1016/j.cemconres.2022.106758

Cementation of aqueous radioactive waste contaminated with a significant Sr is challenging, and utilization of calcium aluminate cement (CAC) modified with sodium polyphosphate (CAP) is interesting. The present study investigated solidification and stabilization of Sr and Cl ions in CAC and CAP cured in open system at 90C and in closed system at 20C. A leaching test showed that Sr ion could be stabilized more effectively in the CAP than in the CAC. On the other hand, the CAC cured at 20C had the best stabilization for Cl ion among the samples. Friedel's salt formed in the CAC may have contributed to the immobilization of Cl ion. Although the stabilization of Cl ion by CAP was less effective than CAC, it was significantly improved by the thermal treatment. The results may suggest that Cl ion in the CAP was incorporated in the poorly crystalline apatite structure.

Application of phosphate modified CAC for incorporation of simulated secondary aqueous wastes in Fukushima Daiichi NPP, 1; Characterization of solidified cementitious systems with reduced water content

Garcia-Lodeiro, I.*; Lebon, R.*; Machoney, D.*; Zhang, B.*; Irisawa, Keita; Taniguchi, Takumi; Namiki, Masahiro*; Osugi, Takeshi; Meguro, Yoshihiro; Kinoshita, Hajime*

Proceedings of 3rd International Symposium on Cement-based Materials for Nuclear Wastes (NUWCEM 2018) (USB Flash Drive), 4 Pages, 2018/11

Effect of chloride ion on corrosion behavior of SUS316L-grade stainless steel in nitric acid solutions containing seawater components under -ray irradiation

Sano, Yuichi; Ambai, Hiromu; Takeuchi, Masayuki; Iijima, Shizuka; Uchida, Naoki

Journal of Nuclear Materials, 493, p.200 - 206, 2017/09

https://doi.org/10.1016/j.jnucmat.2017.06.017

Concerning the Fukushima Daiichi Nuclear Power Plant accident, we investigated the effect of chloride ion on the corrosion behavior of SUS316L stainless steel, which is a typical material for the equipment used in reprocessing, in HNO solution containing seawater components, including under the -ray irradiation condition. Electrochemical and immersion tests were carried out using a mixture of HNO and artificial seawater (ASW). In the HNO solution containing high amounts of ASW, the cathodic current densities increased and uniform corrosion progressed. This might be caused by strong oxidants, such as Cl and NOCl, generated in the reaction between HNO and Cl ions. The corrosion rate decreased with the immersion time at low concentrations of HNO, while it increased at high concentrations. Under the -ray irradiation condition, the corrosion rate decreased due to the suppression of the cathodic reactions by the reaction between the above oxidants and HNO generated by radiolysis.

Verification of alternative dew point hygrometer for CV-LRT in MONJU; Short- and long-term verification for capacitance-type dew point hygrometer (Translated document)

Ichikawa, Shoichi; Chiba, Yusuke; Ono, Fumiyasu; Hatori, Masakazu; Kobayashi, Takanori; Uekura, Ryoichi; Hashiri, Nobuo*; Inuzuka, Taisuke*; Kitano, Hiroshi*; Abe, Hisashi*

JAEA-Research 2017-001, 40 Pages, 2017/03

JAEA-Research-2017-001.pdf:5.19MB

In order to reduce the influence on a plant schedule of the MONJU by the maintenance of dew point hygrometers, The JAEA examined a capacitance type dew point hygrometer as an alternative dew point hygrometer for a lithium-chloride type dew point hygrometer which had been used at the CV-LRT in the MONJU. As a result of comparing a capacitance type dew point hygrometer with a lithium-chloride type dew point hygrometer at the CV-LRT (Atmosphere: nitrogen, Testing time: 24 hours), there weren't significant difference between a capacitance type dew point hygrometer and a lithium-chloride type dew point hygrometer. As a result of comparing a capacitance dew point hygrometer with a high-mirror-surface type dew point hygrometer for long term verification (Atmosphere: air, Testing time: 24 months), the JAEA confirmed that a capacitance type dew point hygrometer satisfied the instrument specification (2.04C) required by the JEAC4203-2008.

Chlorination of UO and (U,Zr)O solid solution using MoCl

Sato, Takumi; Shibata, Hiroki; Hayashi, Hirokazu; Takano, Masahide; Kurata, Masaki

Journal of Nuclear Science and Technology, 52(10), p.1253 - 1258, 2015/10

https://doi.org/10.1080/00223131.2015.1070110

In order to explore the applicability of the chlorination by MoCl as a potential pretreatment technique for waste treatment of fuel debris by pyrochemical methods, chlorination experiments of UO and (UZr)O simulated fuel debris were carried out in two steps: the first one is a chlorination reaction by homogeneous heating, the second one is a volatilization of molybdenum by-product by heating under temperature gradient condition. Most of UO and (UZr)O powder were converted to UCl or UCl and ZrCl mixture at 573 K, respectively. In the case of (UZr)Osintered particle, most of sample was converted to the chlorides because the products evaporated and be separated from sample surface at 773 K, while only the surface of the sample disk was converted to the chlorides at 573 and 673 K. Most of molybdenum by-product and ZrCl were separated from UCl by volatilization at 573 K.

Dyed Polyvinyl Chloride films for use as high-dose routine dosimeters in radiation processing

Mai, H. H.*; Duong, N. D.*; Kojima, Takuji

Radiation Physics and Chemistry, 69(5), p.439 - 444, 2004/04

https://doi.org/10.1016/j.radphyschem.2003.08.006

Characteristics of the polyvinyl chloride films containing 0.11wt% of malachite green oxalate or 6GX-setoglausine with 100m in thickness were studied for use as routine dosimeters in radiation processing. These films show basically color bleaching under Co -ray irradiation in a dose range of 5 to 50 kGy. The sensitivity of the dosimeters and the linearity of dose response curves are improved by adding 2.5% of chloral hydrate [CClCH(OH)] and 0.15% hydroquinone [HOCHOH]. These additions extent the minimum dose limit to 1 kGy covering dosimetric quality assurance in radiation processing of food and healthcare products. The dose responses of both films at irradiation temperatures of 20-35C are constant relative to those at 25C, and the irradiation temperature coefficients for 35-55C were estimated to be (0.43 0.01)%/ C. The dosimeter characteristics are stable within 1% at 25C before and 60 days after irradiation.

Local structure of molten LaCl by K-absorption edge XAFS

Okamoto, Yoshihiro; Shiwaku, Hideaki; Yaita, Tsuyoshi; Narita, Hirokazu; Tanida, Hajime*

Journal of Molecular Structure, 641(1), p.71 - 76, 2002/10

https://doi.org/10.1016/S0022-2860(02)00329-0

The local structure of molten LaCl was investigated by X-ray absorption fine structure(XAFS) of the La K-edge. The nearest La-Cl distance andcoordination number were 2.89 and 7.4 from the curve fitting of the 1st peak in the fourier transform magnitude . The coordination number larger than 6 suggests that the local structure of molten LaCl is not a simple octahedral coordination (LaCl), but 7-fold (LaCl) and/or 8-fold (LaCl) complexes. The 1st La-La distance, of which correlation was observed as a weak 2nd peak in the , was evaluated to be 4.9. It suggests that the distorted corner-sharing connection of the complex species is predominant in the melt, inontrast with molten YCl in which the edge-sharing connection of the 6-fold (YCl) mainly exists.

The Resonance raman effect of dicaesium uranyl tetrachloride in dimethyl sulfoxide

Soga, Takeshi

Spectrochimica Acta, Part A, 57(9), p.1767 - 1780, 2001/08

no abstracts in English

The Resonance Raman effet of uranyl chloride in demethyl sulfoxide

Soga, Takeshi

Spectrochimica Acta, Part A, 56(1), p.79 - 89, 2000/01

no abstracts in English