Optimization of dissolved hydrogen concentration for mitigating corrosive conditions of pressurised water reactor primary coolant under irradiation, 2; Evaluation of electrochemical corrosion potential

Hata, Kuniki; Hanawa, Satoshi; Chimi, Yasuhiro; Uchida, Shunsuke; Lister, D. H.*

Journal of Nuclear Science and Technology, 60(8), p.867 - 880, 2023/08

https://doi.org/10.1080/00223131.2022.2127955

One of the major subjects for evaluating the corrosive conditions in the PWR primary coolant was to determine the optimal hydrogen concentration for mitigating PWSCC without any adverse effects on major structural materials. As suitable procedures for evaluating the corrosive conditions in PWR primary coolant, a couple of procedures, i.e., water radiolysis and ECP analyses, were proposed. The previous article showed the radiolysis calculation in the PWR primary coolant, which was followed by an ECP study here. The ECP analysis, a couple of a mixed potential model and an oxide layer growth model, was developed originally for BWR conditions, which was extended to PWR conditions with adding Li (Na) and H effects on the anodic polarization curves. As a result of comparison of the calculated results with INCA in-pile-loop experiment data as well as other experimental data, it was confirmed that the ECPs calculated with the coupled analyses agreed with the measured within 100mV discrepancies.

Development of a new corrosion mitigation technology using nanobubbles toward corrosion mitigation in PCV system under the influence of //-rays radiolysis (Contract research); FY2020 Nuclear Energy Science & Technology and Human Resource Development Project

Collaborative Laboratories for Advanced Decommissioning Science; Tohoku University*

JAEA-Review 2022-002, 85 Pages, 2022/06

JAEA-Review-2022-002.pdf:3.39MB

The Collaborative Laboratories for Advanced Decommissioning Science (CLADS), Japan Atomic Energy Agency (JAEA), had been conducting the Nuclear Energy Science & Technology and Human Resource Development Project (hereafter referred to "the Project") in FY2020. The Project aims to contribute to solving problems in the nuclear energy field represented by the decommissioning of the Fukushima Daiichi Nuclear Power Station, Tokyo Electric Power Company Holdings, Inc. (TEPCO). For this purpose, intelligence was collected from all over the world, and basic research and human resource development were promoted by closely integrating/collaborating knowledge and experiences in various fields beyond the barrier of conventional organizations and research fields. The sponsor of the Project was moved from the Ministry of Education, Culture, Sports, Science and Technology to JAEA since the newly adopted proposals in FY2018. On this occasion, JAEA constructed a new research system where JAEA-academia collaboration is reinforced and medium-to-long term research/development and human resource development contributing to the decommissioning are stably and consecutively implemented. Among the adopted proposals in FY2020, this report summarizes the research results of the "Development of a new corrosion mitigation technology using nanobubbles toward corrosion mitigation in PCV system under the influence of //-rays radiolysis" conducted in FY2020. In this work, in order to ensure the long-term reliability of steel structures that ensure important confinement functions in the debris removal process, such as existing PCVs and newly constructed negative pressure maintenance systems and piping, corrosion phenomena in wet environments where - and -ray emitting nuclides come into contact with steel are clarified for the first time.

Radiation-induced effects on the extraction properties of hexa--octylnitrilo-triacetamide (HONTA) complexes of americium and europium

Toigawa, Tomohiro; Peterman, D. R.*; Meeker, D. S.*; Grimes, T. S.*; Zalupski, P. R.*; Mezyk, S. P.*; Cook, A. R.*; Yamashita, Shinichi*; Kumagai, Yuta; Matsumura, Tatsuro; et al.

Physical Chemistry Chemical Physics, 23(2), p.1343 - 1351, 2021/01

https://doi.org/10.1039/D0CP05720G

The candidate An(III)/Ln(III) separation ligand hexa--octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions using a solvent test loop in conjunction with cobalt-60 gamma irradiation. We demonstrate that HONTA undergoes exponential decay with increasing gamma dose to produce a range of degradation products which have been identified and quantified by HPLC-ESI-MS/MS techniques. The combination of HONTA destruction and degradation product ingrowth, particularly dioctylamine, negatively impacts the extraction and back-extraction of both americium and europium ions. The loss of HONTA was attributed to its reaction with the solvent (-dodecane) radical cation of (HONTA + R) = (7.61 0.82) 10 M s obtained by pulse radiolysis techniques. However, when this ligand is bound to either americium or europium ions, the observed -dodecane radical cation kinetics increase by over an order of magnitude. This large reactivity increase to additional reaction pathways occurring upon metal-ion binding. Lastly nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (100 ns) HONTA radical cation as well as a longer-lived (s) HONTA triplet excited state. These HONTA species are important precursors to the suite of HONTA degradation products observed.

On the hydrogen production of geopolymer wasteforms under irradiation

Cantarel, V.; Arisaka, Makoto; Yamagishi, Isao

Journal of the American Ceramic Society, 102(12), p.7553 - 7563, 2019/12

https://doi.org/10.1111/jace.16642

The hydrogen gas (H) production of wasteforms is a major safety concern for encapsulating nuclear wastes. For geopolymers, the H produced by radiolytic processes is a key factor because of the large amount of water present in their porous structure. Herein, the hydrogen production was measured under Co gamma irradiation. The effect of water saturation and sample size were studied for pure geopolymers, or using zeolites as an example waste. When geopolymer monolithic samples were large and saturated by water, the hydrogen released was measured up to two orders of magnitude lower with a 40 cm long cylinder samples (1.910 mol/J) than a sample in powder form (2.210 mol/J). To interpret results, a simple model was used, considering only hydrogen production, a potential recombination and its diffusion in the geopolymer matrix. Knowing the diffusion constant of the matrix, the model was able to reproduce the evolution of the hydrogen release as a function of the water saturation level and predict the evolution when sample size is increased up to 40 cm.

Radiation-induced degradation of aqueous 2-chlorophenol assisted by zeolites

Kumagai, Yuta; Kimura, Atsushi*; Taguchi, Mitsumasa*; Watanabe, Masayuki

Journal of Radioanalytical and Nuclear Chemistry, 316(1), p.341 - 348, 2018/04

https://doi.org/10.1007/s10967-018-5762-z

We studied effect of adsorption and condensation by zeolites on radiation-induced degradation of aqueous 2-chlorophenol (2-ClPh). This study aims to demonstrate that the solid-phase extraction using zeolites has potential advantage in treatments of aqueous organic pollutants. Among three zeolites examined in this study, a mordenite type zeolite (HMOR) that has a high Si to Al ratio (127 3) exhibited preferable performance as the matrix for the 2-ClPh degradation. HMOR adsorbed far more 2-ClPh than the other zeolites, which have lower Si/Al ratios. The irradiation of HMOR induced degradation of adsorbed 2-ClPh into Cl and organic by-products. We found a significant increase in Cl production by HMOR. The yield of Cl production in the presence of HMOR was as high as the yield in aqueous solution of 2-ClPh at a concentration 10 times higher. The increased Cl production indicates that the high concentration of adsorbed 2-ClPh led to effective use of the adsorbed energy of HMOR.

Study of irradiation effect on ECP using in-pile loops in the JMTR

Hanawa, Satoshi; Uchida, Shunsuke; Hata, Kuniki; Chimi, Yasuhiro; Kasahara, Shigeki*; Nishiyama, Yutaka

Proceedings of 20th Nuclear Plant Chemistry International Conference (NPC 2016) (USB Flash Drive), 10 Pages, 2016/10

The authors proposed and ECP evaluation model introducing irradiation-induced diffusion in the oxide layer to simulate neutron irradiation effect, and predicted with this model that ECP is started to depress from the neutron flux of about ten to the fourteenth per square meter. As the JMTR has in-pile loops applicable to water chemistry experiments, degree of irradiation effect on ECP appears in the in-pile loop was estimated by the model. Under oxygen injected condition, ECP in a capsule becomes constant along the vertical direction due to the presence of high amount of oxygen and hydrogen peroxide in a capsule. However, if neutron irradiation depress ECP, ECP in a capsule along vertical direction wouldn't become constant, and the degree to the decrement is detectable by experiments.

Radiolysis of boiling water

Yang, S.*; Katsumura, Yosuke*; Yamashita, Shinichi*; Matsuura, Chihiro*; Hiroishi, Daisuke*; Lertnaisat, P.*; Taguchi, Mitsumasa

Radiation Physics and Chemistry, 123, p.14 - 19, 2016/06

https://doi.org/10.1016/j.radphyschem.2016.02.008

-radiolysis of boiling water has been investigated. The G-value of H evolution was found to be very sensitive to the purity of water. In high-purity water, both H and O gases were formed in the stoichiometric ratio of 2:1; a negligible amount of HO remained in the liquid phase. The G-values of H and O gas evolution depend on the dose rate: lower dose rates produce larger yields. To clarify the importance of the interface between liquid and gas phase for gas evolution, the gas evolution under Ar gas bubbling was measured. A large amount of H was detected, similar to the radiolysis of boiling water. The evolution of gas was enhanced in a 0.5 M NaCl aqueous solution. Deterministic chemical kinetics simulations elucidated the mechanism of radiolysis in boiling water.

Hydrogen peroxide production by radiolysis of sodium chloride solutions containing a small amount of bromide ion

Hata, Kuniki; Inoue, Hiroyuki*; Kojima, Takao*; Iwase, Akihiro*; Kasahara, Shigeki; Hanawa, Satoshi; Ueno, Fumiyoshi; Tsukada, Takashi

Nuclear Technology, 193(3), p.434 - 443, 2016/03

https://doi.org/10.13182/NT15-32

Effects of -radiation on a direct disposal system for spent nuclear fuel, 2; Review of research into safety assessments of direct disposal of spent nuclear fuel in Europe and North America

Kitamura, Akira; Takase, Hiroyasu*; Metcalfe, R.*; Penfold, J.*

Journal of Nuclear Science and Technology, 53(1), p.19 - 33, 2016/01

https://doi.org/10.1080/00223131.2015.1014874

Not only geological disposal of vitrified waste generated by spent fuel (SF) reprocessing, but also the possibility of disposing of SF itself in deep geological strata (hereinafter "direct disposal of SF") may be considered in the Japanese geological disposal program. In the case of direct disposal of SF, the radioactivity of the waste is higher and the potential effects of the radiation are greater. Specific examples of the possible effects of radiation include: increased amounts of canister corrosion; generation of oxidizing chemical species in conjunction with radiation degradation of groundwater and accompanying oxidation of reducing groundwater; and increase in the dissolution rate and the solubility of SF. Therefore, the influences of radiation, which are not expected to be significant in the case of geological disposal of vitrified waste, must be considered in safety assessments for direct disposal of SF. Focusing especially on the effects of -radiation in safety assessment, this study has reviewed safety assessments in countries other than Japan that are planning direct disposal of SF. The review has identified issues relevant to safety assessment for the direct disposal of SF in Japan.

Influence of radiolysis and gas-liquid partition of I-131 in accumulated water on late phase source terms at Fukushima NPP accident

Hidaka, Akihide

Proceedings of 2014 Nuclear Plant Chemistry Conference (NPC 2014) (USB Flash Drive), 12 Pages, 2014/10

During core cooling at Fukushima Daiichi NPP accident, large amount of contaminated water was accumulated in the basements of reactor buildings at Units 1 to 4. The estimated ratios of I-131 and Cs-137 quantities in water to the core inventories are 0.51%, 0.85% at Unit 1, 74%, 38% at Unit 2 and 26%, 18% at Unit 3, respectively. According to the Henry's law, certain fraction of iodine in water could be released to atmosphere. Many evaluations for I-131 release have been performed so far by MELCOR or the reverse estimation with SPEEDI. The SPEEDI reverse predicted significant release until March 26 while no prediction in MELCOR after March 17. The present study showed that iodine release from accumulated water due to radiolytic conversion from I to I and gas-liquid partition of I may explain the release between March 17 and 26. This strongly suggests a need for improvement of current MELCOR approach which treats the release only from containment breaks.