Otani, Kyohei; Tsukada, Takashi; Ueno, Fumiyoshi; Kato, Chiaki
Zairyo To Kankyo, 69(9), p.246 - 252, 2020/09
The purpose of this study was to investigate the effect of artificial sea water concentration on the corrosion rate of carbon steel under air/solution alternating condition, and to clarify the corrosion mechanism of carbon steel that changes with artificial seawater concentration. Mass measurements showed that the corrosion rate of carbon steel in the alternating condition accelerates with increasing concentration in the concentration region between deionized water to 200 times diluted artificial seawater (ASW), and the corrosion rate decreases with increasing concentration in the concentration region between 20 times diluted ASW to undiluted ASW. It can be considered that the reason why the carbon steel corrosion was suppressed in highly concentrated artificial seawater would Mg ions and Ca ions in the artificial seawater precipitate and cover on the surface due to the increase in pH near the surface by oxygen reduction reaction.
Otani, Kyohei; Tsukada, Takashi; Ueno, Fumiyoshi
Zairyo To Kankyo, 68(8), p.205 - 211, 2019/08
In the present study, the iron rust layer formed on the low ally steel in air-solution alternating condition was investigated by cross-sectional observation and analysis, and the mechanism of accelerated corrosion of the steel in the alternating condition was clarified. Observation and analysis showed that the multi-layered iron rust layer composed of red rust layer (FeOOH), rust crust layer (FeO), inner crystal (FeO), and inner rust layer was formed on the low alloy steel. It can be considered that the multi-layered iron rust layer accelerated the cathodic reaction rate of the steel in the alternating condition. This acceleration would be the reason why the corrosion rate of the low alloy steel in the alternating condition was accelerated.
Zairyo To Kankyo, 68(1), p.2 - 8, 2019/01
It is important to control the cooling water of light water reactors (boiling water reactor and pressurized water reactor) to suitable quality in order to reduce corrosion of structural materials and generation of radioactive corrosion products. For that purpose, monitoring of water quality using electrochemical measurement method is necessary. In this article, the application of ECP measurement to BWR is mainly focused, I describe the water quality of light water reactors and the necessity of electrochemical measurement.
Yamamoto, Masahiro; Soma, Yasutaka; Igarashi, Takahiro; Ueno, Fumiyoshi
Proceedings of Annual Congress of the European Federation of corrosion (EUROCORR 2018) (USB Flash Drive), 7 Pages, 2018/09
In order to clarify the SCC behavior of SUS316L under BWR environment, mass transfer inside crevice of SUS316L in high temperature water using various crevice gap samples was investigated. The samples were prepared by put together two SUS316L sheets. Crevice gap differs from 0.005 mm to 0.1 mm. Corrosion tests were conducted in 8 ppm dissolved oxygen (DO) conditions. Surface oxide film was analysed by laser Raman spectroscopy (LRS) after immersion. Numerical simulations were also conducted by using COMSOL Maltiphysics. Diffusion process of DO and the other chemical species were calculated with connected to electrochemical process. Electrical conductivities inside the crevice were 100 times larger than these of outer water. The reason of high conductivity is existence of Fe ions at the DO depletion crevice.
Yamamoto, Masahiro; Sato, Tomonori; Igarashi, Takahiro; Ueno, Fumiyoshi; Soma, Yasutaka
Proceedings of European Corrosion Congress 2017 (EUROCORR 2017) and 20th ICC & Process Safety Congress 2017 (USB Flash Drive), 6 Pages, 2018/09
The authors have studied the differences between outer surface and the crevice-like portion of SUS316L in high pressurized and high temperature water containing dissolved oxygen. We have already introduced that changes in the characteristics of corrosion products along the crevice directions and gap width. It is suggested that the environmental conditions are different with the features of crevice from these results. In this report, we introduce the changes in oxide films with crevice gaps and comparison with the numerical simulation data utilizing of FEM calculation.
Soma, Yasutaka; Komatsu, Atsushi; Ueno, Fumiyoshi
Zairyo To Kankyo, 67(9), p.381 - 385, 2018/09
In-situ measurement of electrical conductivity of solution within crevice of SUS316L stainless steel in 288C water has been conducted with newly developed electrochemical sensor system. The sensor measures local electrical conductivity of crevice solution beneath the electrode () with electrochemical impedance method. The sensors were installed at different positions within tapered crevice of SUS316L stainless steel. The crevice specimen with the sensors were immerged into 288C, 8 MPa, pure oxygen saturated high purity water for 100 h. at a position with crevice gap of 59.3m was 8-11S/cm, least deviate from conductivity of 288C pure water (4.4S/cm) and no localized corrosion occurred. On the contrary, at a position with crevice gap of 4.4m increased with time and showed maximum value of 1600S/cm at 70 h. Localized corrosion occurred in the vicinity of this position. Thermodynamic equilibrium calculation showed of 1600S/cm being equivalent to pH of 3 to 3.7. It can be concluded that acidification occurred in tight crevice even under high purity bulk water and resulted in localized corrosion.
Soma, Yasutaka; Ueno, Fumiyoshi
Zairyo To Kankyo, 67(5), p.222 - 228, 2018/05
Localized corrosion in crevice of SUS316 stainless steel after immersion in 288C high purity water with dissolved oxygen concentration of 32 ppm for 100 h was analyzed. Two different types of localized corrosion initiated on grain boundary and inclusions. The former initiated on grain boundary and oxide grown into grain matrix. The oxidized area showed duplex structure composed of microcrystalline FeCrO and island-shaped residual metals. The latter initiated on inclusions containing Ca and S and microcrystalline FeCrO grown into metal matrix. These localized corrosion occurred selectively in oxygen depleted area indicated formation of macroscopic corrosion cell with the corroded area as anode and surrounding oxygenated area as cathode.
Soma, Yasutaka; Kato, Chiaki; Ueno, Fumiyoshi
Proceedings of the 18th International Conference on Environmental Degradation of Materials in Nuclear Power Systems - Water Reactors, Vol.2, p.509 - 521, 2018/00
In-situ electrochemical measurement within crevice of stainless steel in 288C water has been conducted to analyze crevice water chemistry. Small sensors ( 250m) measured local solution electrical conductivity, , polarization resistance, and electrochemical corrosion potential. Real-time response of the as functions of bulk water conductivity, dissolved oxygen (DO) concentration has been quantitatively analyzed. The effect of geometrical factors on the crevice environment was also studied. The differ more than an order of magnitude depending on the oxygen potential inside the crevice. The increased by small amount of bulk DO (e.g. 30 ppb). Maximum was observed with DO of 32000 ppb and became more than 100 times higher than that of bulk water. Crevice geometry affected significantly on the water chemistry inside.
Irisawa, Eriko; Kato, Chiaki; Kamoshida, Michio*; Hakamatsuka, Yasuyuki*; Ueno, Fumiyoshi; Yamamoto, Masahiro
Proceedings of European Corrosion Congress 2017 (EUROCORR 2017) and 20th ICC & Process Safety Congress 2017 (USB Flash Drive), 9 Pages, 2017/09
Hata, Kuniki; Inoue, Hiroyuki*; Kojima, Takao*; Kasahara, Shigeki; Hanawa, Satoshi; Ueno, Fumiyoshi; Tsukada, Takashi; Iwase, Akihiro*
Proceedings of Symposium on Water Chemistry and Corrosion in Nuclear Power Plants in Asia 2017 (AWC 2017) (USB Flash Drive), p.304 - 314, 2017/09
A model simulation of radiolysis of mixed solutions of NaCl and NaBr was carried out. The simulation result agreed well with the experimental result, and Br played an important role in determining the amounts of products from water radiolysis. The simulation result also showed that, in highly pure NaCl solutions, the steady-state concentration of a radolytic product, HO, was mainly controlled by three reactions (Cl + OH ClOH, ClOH Cl + OH, and ClOH + H Cl + HO), which indicated that accurate evaluation of the rate constants of these reactions was very important in improving the radiolysis simulation of solutions containing Cl. An immersion test using a low-alloy steel, SQV2A, in the mixed solutions was also carried out under irradiation. The corrosion rate increased or decreased depending on the pH or the concentrations of the halide ions in a similar way to the change in concentration of HO produced from water radiolysis, which is affected by the presence of Cl and Br. However, at high pH values (12), the corrosion rate was almost zero even though the concentration of HO was high. This could be attributed to enhancement of the passivity of test specimens at higher pH values.
Ishijima, Yasuhiro; Ueno, Fumiyoshi; Abe, Hitoshi
Nippon Genshiryoku Gakkai Wabun Rombunshi, 16(2), p.100 - 106, 2017/05
Zirconium (Zr) has been used as a structural material at the spent nuclear fuel reprocessing plant in Japan because of its excellent corrosion resistance against nitric acid solution. And the radiolytic hydrogen is known to be generated in the spent nuclear fuel solution. Zr is known to be highly susceptible to hydrogen embrittlement. Therefore, evaluating the radiolytic hydrogen absorption behavior of Zr in nitric acid solution (HNO) is essential. In this study, immersion tests were conducted on Zr in nitric acid solutions under -ray irradiation to evaluate its radiolytic hydrogen absorption behavior. Results showed that hydrogen concentration on Zr increased both in 1-3 mol/L HNO and pure water at 5 and 7 kGy/h after immersion. The amount of hydrogen absorption on Zr under -ray irradiation had a direct correlation with the radiolytic hydrogen generation value in HNO. The results of glow discharge optical emission spectrometry, thermal desorption spectroscopy, and X-ray diffraction result shows that the absorbed radiolytic hydrogen generated a hydride on the surface of Zr.
Soma, Yasutaka; Kato, Chiaki; Ueno, Fumiyoshi
Fushoku Boshoku Kyokai Dai-63-Kai Zairyo To Kankyo Toronkai Koenshu, p.253 - 256, 2016/10
Contribution of corrosion to advance of stress corrosion cracking (SCC) of stainless steel in high temperature water must be assessed because serious corrosion can be found within SCC of light water reactors. The corrosion took the form of both intergranular and grain-matrix attack indicate aggressive corrosion condition was formed in the crevice of the SCC. We have investigated the crevice environment electrochemically and found that local electrical conductivity of the crevice solution at satisfactory narrow crevice gap having more than 100 times higher than that of bulk solution. In this research we assessed effect of cyclic deaerated and aerated bulk solution to the crevice environment. The result showed that electrical conductivity of the crevice solution under the deaerated bulk solution increased more than 10times by injection of pure oxygen suggest that the dissolved oxygen caused aggressive corrosion condition within the crevice.
Kato, Chiaki; Ishijima, Yasuhiro; Ueno, Fumiyoshi; Yamamoto, Masahiro
Journal of Nuclear Science and Technology, 53(9), p.1371 - 1379, 2016/09
The effects of crystal textures and the potentials in the anodic oxidation of zirconium in a boiling nitric acid solution were investigated to study the stress corrosion cracking of zirconium in nitric acid solutions. The growth of the zirconium oxide film dramatically changed depending on the applied potential at a closed depassivation potential (1.47 V vs. SSE). At 1.5 V, the zirconium oxide film rapidly grows, and its growth exhibits cyclic oxidation kinetics in accordance with a nearly cubic rate law. The zirconium oxide film grows according to the quantity of electric charge, and the growth rate does not depend on the crystal texture in the pretransition region before the cyclic oxidation kinetics. However, the growth and cracking under the thick oxide film depend on the crystal texture in the transition region. On the normal direction side, the oxide film thickness decreases on average since some areas of the thick oxide film are separated from the specimen surface owing to the cracks in the thick oxide. On the rolling direction side, cracks are found under the thick oxide film, which deeply propagate along the RD without an external stress. The cracks under the thick oxide film propagate to the center of the oxide layer. The cracks in the oxide layer propagate in the (0002)Zr plane in the zirconium matrix. The oxide layer consists of string-like zirconium oxide and zirconium hydride. The string-like zirconium oxide contains orthorhombic ZrO in addition to monoclinic ZrO. As one assumption for the mechanism of crack initiation and propagation without an external stress, it is considered that the oxidizing zirconium hydrides precipitate in the (0002)Zr and then the phase transformation from orthorhombic ZrO to monoclinic ZrO in the oxide layer causes the crack propagation in the (0002) plane.
Motooka, Takafumi; Ueno, Fumiyoshi; Yamamoto, Masahiro
Proceedings of 2016 EFCOG Nuclear & Facility Safety Workshop (Internet), 6 Pages, 2016/09
At the Fukushima Daiichi nuclear accident, seawater was injected into spent fuel pools of Unit 2-4 for the emergency cooling. Seawater might cause localized corrosion of spent fuel cladding. This would lead to leakage of not only fissile materials but also fission products from fuel cladding. The behavior, however, is not understood well. In this paper, the effects of seawater on corrosion behavior and mechanical property of were studied by using a spent fuel cladding from a BWR. We immersed the spent cladding tubes in diluted artificial seawater for 300h at 353 K, and conducted their visual, cross-sectional and strength examinations. As a localized corrosion index, the pitting potentials of specimens fabricated from the cladding were measured as functions of chloride ion concentration ranging from 20 to 2500 ppm. The visual examination showed that localized corrosion has not occurred, and cross-sectional examination showed no cracks. The strength of immersed tubes was comparable to that of non-immersed tubes. Additionally, pitting potential could not be measured over 1.0 V; pitting corrosion was hardly occurred. These results suggested that the specimens from the spent fuel cladding tube was very resistant to localized corrosion.
Ueno, Fumiyoshi; Irisawa, Eriko; Kato, Chiaki; Igarashi, Takahiro; Yamamoto, Masahiro; Abe, Hitoshi
Proceedings of European Corrosion Congress 2016 (EUROCORR 2016) (USB Flash Drive), 7 Pages, 2016/09
In this study, we focused on the effect of the boiling of nitric acid solution on the corrosion of a stainless steel-made concentrator in reduced pressure in fuel reprocessing plant. In order to perform the simulation test in a non-radioactive condition, nitric acid solution with the addition of vanadium as an oxidizing metal ion were used. Corrosion tests were carried out under the conditions of boiling at reduced pressure, and of non-boiling at normal pressure and several temperatures. As a result, corrosion was accelerated by the solution boiling while it was not by non-boiling at the same temperature. It was found also that the temperature dependence of corrosion rate is the same in the both conditions of boiling and non-boiling. The corrosion accelerating effect will be discussed on the basis of the reaction among nitric acid, NOx and vanadium, etc.
Hata, Kuniki; Sato, Tomonori; Motooka, Takafumi; Ueno, Fumiyoshi; Hanawa, Satoshi; Kasahara, Shigeki; Tsukada, Takashi
Journal of Nuclear Science and Technology, 53(8), p.1183 - 1191, 2016/08
Kato, Chiaki; Sato, Tomonori; Ueno, Fumiyoshi; Yamagishi, Isao
Proceedings of 17th International Conference on Environmental Degradation of Materials in Nuclear Power Systems - Water Reactors, Vol.2, p.1357 - 1374, 2016/05
With respect to the long-term storage of the zeolite-containing spent Cs adsorption vessels used at the Fukushima Daiichi Nuclear Power Station, the corrosion of the vessel material is one of the most important issues. In this study, we performed electrochemical tests on stainless steel specimens in zeolite-containing artificial seawater under gamma-ray irradiation. The spontaneous potential ESP and critical pitting potential VC of the type 316L steel in systems in contact with various zeolites were measured in order to evaluate the corrosion resistance of the steel. In addition, the water sample was analyzed after being irradiated, in order to determine the concentrations of various dissolved oxidants such as oxygen and hydrogen peroxide, which can accelerate the corrosion process. The steady-state rest potential increased with an increase in the dose rate; however, the increase was suppressed in contact with the zeolites. The VC value of the steel when in contact with the zeolites was slightly smaller than the VC value in bulk water; however, the choice of the zeolite used as herschelite, IE96 and IE911 hardly affect the VC value. The concentration of HO in the bulk water under irradiation also increased with the increase in the dose rate. This increase was suppressed in the systems in contact with the zeolites, owing to the decomposition of the HO by the zeolites. A clear relationship was observed between ESP and the HO concentration. As contact with the zeolites caused the increase in ESP under irradiation to be suppressed, it can be concluded that the presence of zeolites in the spent Cs adsorption vessels can reduce the probability of the localized corrosion of the stainless steel in the vessels.
Irisawa, Eriko; Ueno, Fumiyoshi; Kato, Chiaki; Abe, Hitoshi
Zairyo To Kankyo, 65(4), p.134 - 137, 2016/04
In order to investigate the effect of boiling under reduced pressure on corrosion of stainless steel in the nitric acid solution, the corrosion tests simulating the high-level radioactive liquid waste evaporator were performed. The results of immersion tests of stainless steels in the solution with and without boiling showed that the corrosion rates in boiling solution were larger than those in not boiling solution in case of same temperature of solution. Moreover, the cathode polarization curves showed that the corrosion potential of stainless steel in boiling solutions were shifted nobler, and the current intensity became larger than that in not boiling solutions. According to these results, it can be concluded that boiling of solution under reduced pressure accelerate the corrosion rates.
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
Yamamoto, Masahiro; Komatsu, Atsushi; Sato, Tomonori; Nakano, Junichi; Ueno, Fumiyoshi
Proceedings of 17th Asian Pacific Corrosion Control Conference (APCCC-17) (USB Flash Drive), 8 Pages, 2016/01
In Fukushima-Daiichi Nuclear Power Station, decommissioning procedures are continuing more than 30 years until fuel debris removal. It is important to keep soundness of primary container vessel (PCV), made of carbon steel, during these procedures. Corrosion of carbon steel is well-known to be controlled by cathodic reaction, in usual, oxygen reduction reaction. Corrosion of carbon steel could be mitigated by nitrogen injection procedure. However, a lot of radioactive materials exist in cooling water, an effect of radiolysis product on corrosion is an important problem. Clarifying an irradiation effect for corrosion of carbon steel, corrosion test was conducted in Co -ray irradiated condition. Electrochemical measurements were conducted to determine cathodic current density of samples. Corrosion rates of carbon steel decrease with time in both -ray irradiated and non-irradiated conditions. Measured values of cathodic current density gradually decreased with time and then stayed at constant value.