Contrast dependence of scattering profiles for poly(ethylene glycol) in water; Investigation by small-angle neutron scattering with He spin filter and small-angle X-ray scattering

Ryoki, Akiyuki*; Watanabe, Fumi*; Okudaira, Takuya*; Takahashi, Shingo*; Oku, Takayuki; Hiroi, Kosuke; Motokawa, Ryuhei; Nakamura, Yo*

Journal of Chemical Physics, 160(11), p.114907_1 - 114907_9, 2024/03

https://doi.org/10.1063/5.0192680

Effects of potential on the electrical conductivity of a solution within a crevice of stainless steel in high-temperature water

Soma, Yasutaka; Komatsu, Atsushi; Ueno, Fumiyoshi

Corrosion, 78(6), p.503 - 515, 2022/06

https://doi.org/10.5006/3187

The effects of electrochemical potential (ECP) on water chemistry within a crevice are of critical importance for understanding stress corrosion cracking (SCC) of Fe-Cr-Ni alloys in high temperature water. In this study, the effects of ECP on the electrical conductivity of a solution within a Type-316L stainless steel crevice () have been studied in 288C and 8 MPa water containing 10 ppb Cl as major anionic species. In situ measurements of in a rectangular crevice with a gap of 15 m and a depth of 23 mm have been conducted using small sensors installed at different crevice depths. An increase in ECP from -0.49 V (vs. standard hydrogen electrode) to -0.12 V resulted in an increase in from 12 Scm to 160 Scm at a distance of 21 mm from the crevice mouth. The increase in reached a maximum at about 0.15 V (about 300 Scm) and then tended to decrease with increasing potential. Finite element model analysis taking into account the electrochemical reaction quantitatively reproduced this behavior. It is considered that Cl is the major anionic species transported into the crevice at relatively low potentials, and that increases monotonically with increasing ECP. On the other hand, when ECP exceeds around 0 V, a sufficient amount of HCrO generated by transpassive dissolution also transported into the gap. Since this chemical species is highly oxidizing, unlike Cl, it is assumed that it reacts with metal cations to oxidize and precipitate them, thereby lowering conductivity.

Structure of an aqueous RbCl solution in the gigapascal pressure range by neutron diffraction combined with empirical potential structure refinement modeling

Zhang, W. Q.*; Yamaguchi, Toshio*; Fang, C. H.*; Yoshida, Koji*; Zhou, Y. Q.*; Zhu, F. Y.*; Machida, Shinichi*; Hattori, Takanori; Li, W.*

Journal of Molecular Liquids, 348, p.118080_1 - 118080_11, 2022/02

https://doi.org/10.1016/j.molliq.2021.118080

The ion hydration and association and hydrogen-bonded water structure in an aqueous 3 mol/kg RbCl solution were investigated at 298 K/0.1 MPa, 298 K/1 GPa, 523 K/1 GPa, and 523 K/4 GPa by neutron diffraction combined with EPSR methods. The second hydration layer of Rb and Cl becomes evident under elevated pressure and temperature conditions. The average oxygen coordination number of Rb (Cl) in the first hydration layer increases from 6.3 (5.9) ambient pressure to 8.9 (9.1) at 4 GPa, while decreasing coordination distance from 0.290 nm (0.322 nm) to 0.288 nm (0.314 nm). The orientation of the water dipole in the first solvation shell of Rb and a central water molecule is sensitive to pressure, but that in the first solvation shell of Cl does not change very much. The number of contact-ion pairs Rb-Cl decreases with elevated temperature and increases with elevated pressure. Water molecules are closely packed, and the tetrahedral hydrogen-bonded network of water molecules no longer exists in extreme conditions.

Hydrogen absorption mechanism into iron in aqueous solution including metal cations by laser ablation tests and first-principles calculations

Igarashi, Takahiro; Otani, Kyohei; Kato, Chiaki; Sakairi, Masatoshi*; Togashi, Yusuke*; Baba, Kazuhiko*; Takagi, Shusaku*

ISIJ International, 61(4), p.1085 - 1090, 2021/04

https://doi.org/10.2355/isijinternational.ISIJINT-2020-065

In order to clarify the effect of metal cations (Zn, Mg, Na) in aqueous solution on hydrogen permeation into iron, the amount of hydrogen permeation from iron surface was measured by electrochemical tests with a laser ablation. Moreover, in order to obtain the basic mechanism of hydrogen permeation with metal cation, first-principles calculations were used to acquire the adsorption potential of the metal cation and the electronic state around iron surface. By Zn in solution, anodic reaction on ablated surface by laser irradiation was suppressed. Also, by quantum analysis Zn atoms were chemically bonded stronger than Na and Mg atoms to iron surface. It was suggested that the dissolution reaction of iron was suppressed by the formation of the Zn layer, and that lead suppression of hydrogen permeation into iron.

Evaluation of the characteristics of metal nitrate aqueous solutions by microwave heating and the morphologies of synthesized metal oxide powders

Segawa, Tomoomi; Kawaguchi, Koichi; Ishii, Katsunori; Suzuki, Masahiro; Fukasawa, Tomonori*; Fukui, Kunihiro*

Funtai Kogakkai-Shi, 57(9), p.485 - 494, 2020/09

In the spent fuel reprocessing process, a mixed solution of uranyl nitrate and plutonium nitrate is converted into mixed oxide powder by the microwave heating. To evaluate the applicability to the industrial-scale and acquire the characteristics data of the microwave heating denitration of various metal nitrate aqueous solutions based on the knowledge studied in the development of laboratory-scale basic experiments, the microwave heating characteristics and metal oxide powder properties were investigated using cerium nitrate, cobalt nitrate and copper nitrate aqueous solutions. The progress rate of the denitration reaction was depended on the position, and the denitration reaction proceeded faster at the periphery than at the center. The morphologies of the synthesized products were porous and hard dry solid with cerium nitrate aqueous solution, foamed dry solid with cobalt nitrate aqueous solution, and powdery particles with copper nitrate aqueous solution. The denitration ratio and average particle size of the synthesized products increased in the order of the cerium nitrate aqueous solution, the cobalt nitrate aqueous solution, and the copper nitrate aqueous solution. The numerical simulations revealed that the periphery of the bottom surface of the metal nitrate aqueous solution was heated by microwaves. This results consistent with the experimental results in which the denitration reaction started from the periphery of the metal nitrate aqueous solution.

Study on characterization of colloidal silica grout for rock excavation under saline groundwater

Tsuji, Masakuni*; Nakashima, Hitoshi*; Saito, Akira*; Okihara, Mitsunobu*; Sato, Toshinori

45th Annual Waste Management Conference (WM 2019); Encouraging Young Men & Women to Achieve Their Goals in Radwaste Management, Vol.7, p.4749 - 4763, 2020/01

A rock excavation grouting technology has been recently studied as significant technology for reducing the ingress of water into the deep repository. However, it has not been studied for applying to the coastal region, where it is discussed to be a more suitable region for the geological disposal in Japan. The latest material called colloidal silica grout (CSG) is good for sealing narrow fractures but is known to be sensitive to the salinity of groundwater because of its gelling property with salt accelerator. Although the gelling of CSG can be controlled by adding an acidic pH adjuster, the methodology for delivering the appropriate grout is not well established for such conditions of saline groundwater. Therefore, this research project was established to enhance the existing rock grouting technology for deep repositories.

Ion hydration and association in an aqueous calcium chloride solution in the GPa range

Yamaguchi, Toshio*; Nishino, Masaaki*; Yoshida, Koji*; Takumi, Masaharu*; Nagata, Kiyofumi*; Hattori, Takanori

European Journal of Inorganic Chemistry, 2019(8), p.1170 - 1177, 2019/02

https://doi.org/10.1002/ejic.201900016

Neutron diffraction measurements of an aqueous 2 mol dm CaCl solutions in DO have been made at 1 GPa, 298 K as well as 0.1 MPa, 298 K. The experimental structure factors are subjected to Empirical Potential Structure Refinement (EPSR) modeling to reveal the ion hydration and association and solvent water at the atomic level. About seven water molecules surround Ca at the Ca-O and Ca-D distances of 2.44 and 3.70 , respectively, at both pressures, suggesting no significant pressure effect on the cation hydration. On the other hand, the Cl ion shows a drastic change in water oxygen coordination from 7 at 0.1 MPa to 14 at 1 GPa, accompanied by shortening of Cl-O distance from 3.18 to 3.15 . However, the number of water hydrogen atoms around Cl does not change significantly as 6.0 6.7 with shortening Cl-D distance from 2.22 to 2.18 on compression. The pressure effect on the solvent water structure is also drastic as an increase in water oxygen atoms of 4.7 at the O-O distance of 2.79 at 0.1 MPa to 10.3 at 2.85 at 1 GPa. The number of water hydrogen atoms, however, does not change as 1.2 at the O-D distance of 1.74 for both pressures, demonstrating the presence of the OD hydrogen bonds which are significantly bent at 1 GPa at 298 K. This change of hydrogen bonds in water with pressure probably causes the drastic increase in water oxygen atoms around Cl.

Study on characterisation of colloidal silica grout under condition of sea water

Toguri, Satohito*; Okihara, Mitsunobu*; Tsuji, Masakuni*; Nakashima, Hitoshi*; Sugiyama, Hirokazu*; Saito, Akira*; Sato, Toshinori; Aoyagi, Kazuhei; Masunaga, Kosuke

JAEA-Research 2017-013, 131 Pages, 2018/02

JAEA-Research-2017-013.pdf:8.49MB

The discussions on scientifically promising site for the geological disposal has been made at the council of studying group on techniques for geological disposal of radioactive wastes, which is held by Resources and Energy Agency. From the aspect of ensuring safety during the transportation of disposal waste, the coastal area is discussed to be a more suitable area. This report shows the result of the first year of this project as following items; Study on the state-of-art technology and remain tasks; laboratory tests on characterization of colloidal silica grout under sea water; Study on the development of grouting technology (design and the evaluation method of influence on the rock mass).

Effect of chloride concentration on corrosion behavior of carbon steel under -ray irradiation

Motooka, Takafumi; Ueno, Fumiyoshi

Zairyo To Kankyo, 64(6), p.220 - 223, 2015/06

http://doi.org/10.3323/jcorr.64.220

Corrosion behavior of carbon steel in chloride aqueous solutions under a low dose rate was investigated by corrosion test using chloride aqueous solutions with different chloride concentration at a dose rate of 500 Gy/h. The corrosion rate of carbon steel increased by the irradiation, and the corrosion rate had the maximum value at a certain chloride concentration. The oxidants produced by radiolysis of chloride aqueous solution enhanced the corrosion of carbon steel. The main oxidants were oxygen and hydrogen peroxide, and the diffusion process of oxidants controlled the corrosion of carbon steel under irradiation. There was a positive correlation between the dependence of corrosion rate and chloride concentration and the dependence of oxidant concentration and chloride concentration.

Curium(III) species and the coordination states in concentrated LiCl-aqueous solutions studied by time-resolved laser-induced fluorescence spectroscopy

Arisaka, Makoto; Kimura, Takaumi; Nagaishi, Ryuji; Yoshida, Zenko

Journal of Alloys and Compounds, 408-412, p.1307 - 1311, 2006/02

https://doi.org/10.1016/j.jallcom.2005.04.127

no abstracts in English