Hydrogen and Hydrazine Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors, (VI) The Effect of Ammonia on Intergranular Stress Corrosion Cracking

Hydrogen and hydrazine co-injection into a boiling water reactor was considered as a new mitigation method of stress corrosion cracking (SCC). In this method, some amount of ammonia will be formed by the decomposition of hydrazine. The effect of ammonia on SCC susceptibility was studied over a wide range of electrochemical corrosion potentials (ECPs) in 288_C water by conducting slow strain rate technique SCC experiments (SSRTs). ECP was changed from _0:6V versus the standard hydrogen electrode (V(SHE)) to 0.1 V(SHE) by controlling dissolved oxygen concentration. Ammonia concentration was controlled to have values of 100 and 530 ppb. Similarly, sulfuric acid was injected to confirm the difference in the effect of injected chemical compounds on SCC susceptibility. The intergranular stress corrosion cracking (IGSCC) fraction, which was used as the index of SCC susceptibility, decreased with decreasing ECP for the case of no chemical injection. Sulfuric acid enhanced the IGSCC fraction. These data were in good agreement with literature data. On the other hand, ammonia at less than 530 ppb did not affect IGSCC fraction. It is expected that 51–280 ppb hydrazine and 0–53 ppb hydrogen will be injected into reactor water to mitigate SCC in BWRs. In the bottom region of the reactor pressure vessel, ECP and ammonia concentration will be _0:1 V(SHE) and 15–60 ppb, respectively. Under these conditions, ammonia did not affect SCC susceptibility. So SCC susceptibility will be mitigated by decreasing the ECP using hydrazine and hydrogen co-injection.     

Hydrazine and Hydrogen Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors, (III)

The effects of hydrazine on the corrosion of Zircaloy-2 were examined in supercritical water. Hydrazine could be used as a reducing agent to control the corrosive environment for the coolant of boiling water reactors (BWRs). Before the corrosion test, the applicability of supercritical water for corrosion testing of zirconium alloys was studied. Supercritical water was found to be a useful solvent for testing corrosion based on the following facts: (1) the weight gain of Zircaloy-2 in supercritical water followed the same cubic law with the activation energy of 133 kJ/mol as that in water and steam did, and (2) the weight gain in supercritical water at 723 K and 24.5 MPa was more than 8 times greater than that in water at 561 K and 7.8 MPa depending on immersion time. The corrosion tests in supercritical water at 723 K and 24.5 MPa under γ-irradiation for 1,000 h were conducted to study the effects of adding nitrogen and ammonia on the corrosion of Zircaloy-2. Nitrogen and ammonia are decomposed products of hydrazine. The measured weight gain, oxide film thickness, and amount of hydrogen pick-up had slight differences between cases with and without the additives. Based on these data, it was concluded adding hydrazine to the coolant has little influence on the corrosion of Zircaloy-2 used in BWR cores.     

The Efficiency of Noble Metals in Reducing the Corrosion Potential in the Primary Coolant Circuits of Boiling Water Reactors Operating under Hydrogen Water Chemistry Operation

In order to promote the effectiveness of hydrogen water chemistry (HWC) and to achieve a more effective reduction in electrochemical corrosion potential (ECP) in the primary coolant circuits of boiling water reactors (BWRs), the technology of noble metal chemical addition (NMCA) was brought into practice about 10 years ago. NMCA aims at enhancing the oxidation of hydrogen on metal surfaces and lowering the concentrations of the oxidants (oxygen and hydrogen peroxide) via recombination with hydrogen on the catalyzed surfaces, and therefore reducing the corrosion potentials of the structural alloys in a BWR primary heat transport circuit. Previous research indicates that the effectiveness of NMCA in combination with a low HWC might be evaluated via model predictions of the hydrogen-to-oxidant molar ratio (M_H/O) in the primary coolant circuit. If the M_H/O at a certain location is calculated to be greater than 2, it is justified that the NMCA would be effective in reducing the ECP to much below the critical potential for Intergranular Stress Corrosion Cracking (IGSCC), E_IGSCC, of --0.23 V_SHE. However, this statement is true only when the recombination efficiency of hydrogen with oxygen and/or hydrogen peroxide at the location of interest is 100%. Otherwise, significant amounts of oxidants may still be present, even with a stoichiometric M_H/O of greater than 2. With the aid of a computer model DEMACE, we explored the impact of incomplete recombination and found that the ECP might be reduced under given circumstances, but not to a great extent, and might remain well above E_IGSCC. Accordingly, considerable caution should be exercised upon using the M_H/O as a sole indicator for evaluating the effectiveness of NMCA with low HWC as a means of mitigating IGSCC in a BWR. An important finding of this study is that it is necessary to quantify the recombination efficiencies of hydrogen with oxygen and/or hydrogen peroxide on the noble metal treated stainless steel surfaces in order to qualify the use of M_H/O as an indicator for NMCA effectiveness in the primary coolant circuit of a BWR.     

Electrochemical Corrosion Potential Modeling in the Primary Heat Transport Circuit of the Chinshan Boiling Water Reactor under the Condition of Hydrogen Water Chemistry with Noble Metal Coating

The technique of noble metal treatment, such as noble metal coating (NMC) or noble metal chemical addition, accompanied by a low level hydrogen water chemistry, is being employed by a number of nuclear power plants around the world for mitigating intergranular stress corrosion cracking in the vessel internals of their boiling water reactors (BWRs). A computer model DEM ACE was expanded and employed to assess the effectiveness of NMC throughout the primary heat transport circuit (PHTC) of a BWR. The effectiveness of NMC was justified by the electrochemical corrosion potential (ECP) and crack growth rate (CGR) predictions. In calculating the ECP, enhancing factors for the exchange current densities of redox reactions available from recently published data, were employed. The Chinshan BWR was selected as a model reactor. According to the modeling results, it was found that the effectiveness of NMC in the PHTC of a BWR could vary from region to region at different feedwater hydrogen concentrations. For the selected BWR, NMC was predicted to be of little benefit when the feedwater hydrogen concentration reached 0.9 ppm or over. In particular, the NMC technique proved to be beneficial in reducing ECP and CGR along the PHTC even if the BWR was operated under normal water chemistry.     

Effects of water chemistry and potential distribution on electrochemical corrosion potential measurements in 553 K pure water

The effects of water chemistry distribution on the potential of a reference electrode and of the potential distribution on the measured potential should be known qualitatively to obtain accurate electrochemical corrosion potential (ECP) data in BWRs. First, the effects of oxygen on a platinum reference electrode were studied in 553 K pure water containing dissolved hydrogen (DH) concentration of 26–105 μg kg^?1 (ppb). The platinum electrode worked in the same way as the theoretical hydrogen electrode under the condition that the molar ratio of DH to dissolved oxygen (DO) was more than 10 and that DO was less than 100 ppb. Second, the effects of potential distribution on the measured potential were studied by using the ECP measurement part without platinum deposition on the surfaces connected to another ECP measurement part with platinum deposition on the surfaces in 553 K pure water containing 100–130 ppb of DH or 100–130 ppb of DH plus 400 ppb of hydrogen peroxide. Measured potentials for each ECP measurement part were in good agreement with literature data for each surface condition. The lead wire connecting point did not affect the measured potential. Potential should be measured at the nearest point from the reference electrode in which case it will be not affected by either the potential distribution or the connection point of the lead wire in pure water.     

Effects of Hydrogen Peroxide on Intergranular Stress Corrosion Cracking of Stainless Steel in High Temperature Water, (V)

The difference in electrochemical corrosion potential of stainless steel exposed to high temperature pure water containing hydrogen peroxide (H₂O₂) and oxygen (O₂)is caused by differences in chemical form of oxide films. In order to identify differences in oxide film structures on stainless steel after exposure to H₂O₂ and O₂ environments, characteristics of the oxide films have been examined by multilateral surface analyses, e.g., X-ray diffraction (XRD), Rutherford back scattering spectroscopy (RBS), secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). Preliminary characterization results of oxide films confirmed that the oxide film formed under the H2O2 environment consists mainly of hematite (α-Fe₂O₂), while that under the O₂ environment consists of magnetite (Fe₃O₄). Furthermore oxidation at the very surface of the film is much more enhanced under the H₂O₂ environment than that under the O₂ environment. It was speculated that metal hydroxide plays an important role in oxidation of stainless steel in the presence of H₂O₂. The difference in electric resistance of oxide film causes the difference in anodic polarization properties. It is recommended that several anodic polarization curves for specimens with differently oxidized films should be prepared to calculate ECP based on the Evans diagram.     

Role of Radiation-Induced Grain Boundary Segregation in Irradiation Assisted Stress Corrosion Cracking

Isolation of microstructural and microchemical effects on irradiation assisted stress corrosion cracking (IASCC) was attempted by means of low-dose high-temperature neutron irradiation in a material test reactor to get better understanding on IASCC. Microstructure, grain boundary segregation, hardness and SCC susceptibility were examined on stainless steels irradiated to 0.8 dpa at around 673 K. The irradiation caused well-developed grain boundary segregation without notable hardening or microstructural changes. No IASCC was found in 593 K hydrogenated water whereas the steels were highly susceptible to IASCC in 561 K oxygenated water. The results suggest that grain boundary segregation, probably Cr depletion, is sufficient to cause IASCC in oxygenated water and that other radiation-induced changes such as microstructure and hardening are required for IASCC in hydrogenated water.     

固溶态控氮不锈钢在高温水中的应力腐蚀破裂

采用高温电化学测控和慢应变拉伸实验方法,研究了304NG超低碳控氮不锈钢（固溶态）在250℃高温水中的应力腐蚀破裂（SCC）与电极电位和水中Cl^-浓度的关系,并与316LN控氮不锈钢对比：结果表明,在不同环境下两种不锈钢的SCC敏感性随电极电位的升高而升高,并且存在一个临界电位Ec,当电位高于该Ec时,才发生SCC。该临界电位Ec随水中Cl^-浓度升高而下降,即发生SCC的环境范围扩大。304NG钢在含5mg／L Cl^-的250℃高温水中的Ec处于0～＋200mV标准氢电极（SHE）之间,更高时发生穿晶型SCC,表明该Cl^-浓度下只有在高氧（高电位）环境中才能发生SCC。当Cl^-浓度升高到50mg／L时,Ec降到-700mV（SHE）以下,表明该浓度下即使完好除氧（低电位）也可能发生SCC。316LN的SCC抗力高于304NG,其在含5mg／L Cl^-的高温水中的Ec位于＋300～＋400mV（SHE）之间,主要是穿晶型SCC。     

Japanese Contributions to Fields of Predicting and Combating Environmentally Assisted Cracking (EAC) of Steels in LWR Water

Two major currents of the EAC relevant activities in Japan are reviewed in some chronological manner. One is the studies on the acceleration of fatigue crack growth in LWR. The work was first pioneered early in Japan, and extensive collaborative works have followed interacting with the international activities, which have yielded a clear views on the potential issues of the RPV structural steels used in the domestic NPPs. Another is the development of materials and techniques to combat the stress corrosion cracking of the structural materials in LWR water environment. Extensive collaboration among the government agencies, utilities, industries and academic societies lead the issues to a dramatic solution in rather short period. Both of those two aspects are stressed to have generic significance in the present and future nuclear technology.     

Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (I)

In order to evaluate the effects of hydrogen peroxide (H₂O₂) on intergranular stress corrosion cracking, a high temperature high pressure water loop, which can control H₂O₂ concentration with minimal oxygen (O₂) co-existence, is required. This loop is characterized by

1. A once-through type loop to prevent accumulation of decomposed O₂ in the loop

2. Minimized autoclave volume to prevent bulk thermal decomposition of H₂O₂

3. A polytetrafluoroethylene (PTFE) lining to prevent surface decomposition of H₂O₂, and

4. A H₂O₂ monitoring system with an off-line H₂O₂ detector to determine concentration in the sampled water which is combined with an in-line dissolved O₂ detector to determine the decomposed O₂ concentration.

The authors developed such a loop previously. In the present work, performance tests were carried out and measured data were evaluated by comparing with predicted values to verify whether the target characteristics were met. The measured H₂O₂ remaining in the sampled water agreed with the predicted amount within 5%. It was confirmed that the ratio of H₂O₂ remaining in the loop autoclave was more than 90% and the concentration could be monitored continuously with the in-line dissolved O₂ detector installed after the cooler in the loop. Electrochemical corrosion potential (ECP) and frequency dependent complex impedance were measured successfully by changing H₂O₂ concentration.     

新锆合金碘致应力腐蚀断口研究

利用扫描电镜和EDXA对新锆合金碘致应力腐蚀的断口进行了形貌观察和成分分析。在断口表面发现腐蚀产物、二次裂纹、沿晶开裂和穿晶准解理开裂等应力腐蚀断裂特征,并观察到锆合金碘致应力腐蚀的“沟槽”特征。起裂区为沿晶开裂,在裂纹扩展阶段,开裂以穿晶为主。断口上腐蚀产物的成分主要是氧和锆,局部准解理开裂区域可检测到碘。去应力退火试样上发现了平行轧面的深沟,且沿晶开裂不明显。试验温度升高,断口上的腐蚀产物增多,而且沿晶开裂更容易。碘分压不仅影响腐蚀产物层的厚度,而且碘分压较高时沿晶开裂容易发生。     

Water Quality Control in Primary Cooling System of Crud Concentration Suppressed Boiling Water Reactor, (I)

The No. 2 Unit of Fukushima-Daini Nuclear Power Plant (2F-2; 1,100 MWe) was commercially operated for 10,320 effective full power hours (EFPH) as its first fuel cycle. The basic design concept of the 2F-2 incorporated the following two features:

(1) Application of procedures for reducing shutdown dose rate based on the Japanese Improvement and Standardization Program

(2) Low crud generation to minimize radioactive waste by careful material selection for the primary system.

Thus, it was possible to keep the average Fe concentration in the condensate water at less than 6 ppb during the first fuel cycle. As a result of this low value, the average life of powdered resin precoated prefilters was extended to about a month, and the average chemical regeneration period of the deep bed demineralizers was extended to more than one year.

The water chemistry of the 2F-2 was characterized by low ⁶⁰Co and high ⁵⁸Co radio-activities in the reactor water, which resulted in a low shutdown dose rate determined mainly by ⁵⁸Co depositing on the primary piping. For example, average dose rate around the primary piping just after reactor shutdown was about 70 mR/h, about 75% of which was from ⁵⁸Co depositing on the pipe inner surfaces. The contribution of ⁶⁰Co was about 25%.     

Optimization of Dissolved Hydrogen Concentration for Control of Primary Coolant Radiolysis in Pressurized Water Reactors

Optimization of the dissolved hydrogen concentration in primary coolant of pressurized water reactors has several potential advantages in material integrity and dose reduction. To assess the threshold value of dissolved hydrogen for reducing condition, in-pile loop experiments and radiolysis model calculations were performed. Both experiments and model calculations indicate that the threshold value of dissolved hydrogen for radiolysis is much less than the present control level in pressurized water reactors, and the in-core region is more easily affected by reduced dissolved hydrogen level than the out-of-core region. The measurement of electrochemical corrosion potential of structural material, while varying dissolved hydrogen levels, is desirable in the future to compensate for the uncertainty of the model calculation. For this purpose, electrochemical corrosion potential of stainless steel at the top-of-core, in which the reference electrode could be inserted, was estimated based on the correlation between the experiments and the modeling for the loop.     

Water Chemistry in a Crack Tip under Irradiation, (II)

Under neutron and gamma-ray irradiations, radiolytic species are generated directly in the crack tip, which causes higher oxidant concentrations and subsequently influences crack propagation rate.

A crevice radiolysis model was proposed to estimate the oxidant concentrations in the crack tip water under gamma-ray irradiation. Direct generation of radiolytic species in the crevice water, and their secondary generation and disappearance caused by their interaction with the crevice surface as well as species in the crevice water were included in the model. The diffusion of the radiolytic species through the narrow gap from the bulk water to the crack tip and vice versa were also considered.

Calculation results confirmed that the concentrations of H₂O₂, one of the most important oxidants in BWR environments, in both bulk water and crack tip water under irradiation (energy deposition rate: 0.1 W/cm) were high enough to show high local ECP in both regions under NWC, but were high in the bulk water and low in the crack tip water under HWC. A high H₂ diffusion rate from the bulk to the crack tip enhanced the recombination reaction of H₂O₂ and H₂.     

Water Chemistry Experience of Nuclear Power Plants in Japan

Japanese LWRs have experienced several troubles caused by corrosions of structural materials in the past ca. 20 years of their operational history, among which are increase in the occupational radiation exposures, intergranular stress corrosion cracking (IGSCC) of stainless steel piping in BWR, and steam generator corrosion problems in PWR. These problems arised partly from the improper operation of water chemistry control of reactor coolant systems. Consequently, it has been realized that water chemistry control is one of the most important factors to attain high availability and reliability of LWR, and extensive researches and developments have been conducted in Japan to achieve the optimum water chemistry control, which include the basic laboratory experiments, analyses of plant operational data, loop tests in operating plants and computer code developments. As a result of the continuing efforts, the Japanese LWR plants have currently attained a very high performance in their operation with high availability and low occupational radiation exposures. A brief review is given here on the R & D of water chemistry in Japan     

Stress Corrosion Cracking of Zircaloy-2 Cladding in Iodine Vapor

Iodine stress corrosion cracking of Zircaloy-2 cladding under static tensile stress has been studied over the temperature range of 250~450°C. The lowest iodine concentration required to cause cracking was 0.15 mg iodine per cm³ free volume in test ampoule at 300°C, and 1.1 mg/cm' at 350°C. The minimum circumferential plastic strain to cause failure was about 0.4% for specimen tubes possessing high cracking susceptibility. Softer tubes tolerate more circumferential deformation before they failed. This is attributed to greater margin retained for work hardening, rather than to smaller residual tensile hoop stress. Cracking was also inhibited by the presence of oxygen in the iodine atmosphere, the threshold partial pressures being 28 torr at 300°C and 9 torr at 350°C. Scanning electron micrographs of the fractured surfaces revealed brittle transgranular fracture carrying river patterns on part of the cleavage facets.     

The Influence of Dissolved Hydrogen on the Corrosion of Type 304 Stainless Steels Treated with Inhibitive Chemicals in High Temperature Pure Water

In order to assess the influence of dissolved hydrogen on the intergranular stress corrosion cracking (IGSCC) characteristics of Type 304 stainless steels treated with inhibitive chemicals, electrochemical corrosion potential (ECP) measurements and slow strain rate tensile (SSRT) tests were conducted in high temperature pure water. A number of thermally sensitized specimens were prepared and then pre-oxidized in a 288°C pure water environment with the presence of 300ppb dissolved oxygen for 360h. Most of the specimens were then separately treated with various inhibitive chemicals including powdered zirconium oxide (ZrO₂), powdered titanium oxide (TiO₂), and zirconyl nitrate [ZrO(NO₃)₂] via hydrothermal deposition at 150°C. Test environments with a dissolved oxygen concentration of 300ppb and various dissolved hydrogen concentrations at 288°C were created. Test results showed that the ECPs of the treated specimens were lower than that of the untreated one no matter what the dissolved hydrogen concentration was. In addition, IGSCC was observed on all specimens (treated or untreated) in all tested environments. However, the untreated specimen exhibited lower elongation, shorter failure time, and more secondary cracks on the lateral surfaces. It was therefore suggested that inhibitive chemicals such as ZrO₂, TiO₂, and ZrO(NO₂)₂ did provide a certain degree of enhancement in improving the mechanical behavior of the treated specimens and in prolonging IGSCC initiation times.