Evaluation of corrosion behaviors for reactor pressure vessels/primary containment vessels in Fukushima Daiichi units 1–3 nuclear power plant

Fukushima Daiichi nuclear power plants (1F) were damaged by unprecedented severe accident in the Great East Japan Earthquake on 11 March 2011, and seawater has been injected as an emergency countermeasure for the core cooling. Although, the RPV and PCV were not supposed to be exposed to diluted seawater, they have been exposed to diluted seawater environment or high-moisture environment. Therefore, seawater corrosion has become an important issue. Immersion corrosion tests were performed for low-alloy steel of RPV material and carbon steel of PCV material in 1F cooling-water-simulated environment. As a result, the mass loss by corrosion was reduced with the decreasing temperature and chloride ion concentration. Moreover, the effects of nitrogen deaeration and Na₂WO₄ addition on corrosion protection were remarkable among the selected corrosion countermeasures. In addition, the integrity assessments of RPV and PCV were performed considering the reduction of plate thickness based on corrosion test data and the load condition based on earthquake response analysis results. It had been confirmed that primary stresses for RPV and PCV equipment satisfied with the allowable values until at least 15 years after the accident.     

Effects of hydrazine addition and N2 atmosphere on the corrosion of reactor vessel steels in diluted seawater under gamma-rays irradiation

Seawater was injected into the reactor cores in the Fukushima Daiichi Nuclear Power Station. Corrosion of primary containment vessel (PCV) steel and reactor pressure vessel (RPV) steel is considered to progress until the molten fuel debris is removed. To evaluate durability of the PCV and RPV steels, corrosion tests were conducted in diluted seawater at 50 °C under gamma-rays irradiation of dose rates of 4.4 and 0.2 kGy/h. To evaluate the effect of hydrazine (N₂H₄) as an oxygen scavenger under gamma-rays irradiation, 10 and 100 mg/L N₂H₄ were added to the diluted seawater. Without addition of N₂H₄, weight loss in the PCV and RPV steels irradiated with the 0.2 kGy/h dose rate was comparable with those without irradiation and weight loss in the vessel steels irradiated with the 4.4 kGy/h dose rate was higher than those without irradiation. Under irradiation, weight loss in the PCV and RPV steels in diluted seawater containing N₂H₄ was comparable with that in diluted seawater without N₂H₄. When gas phase in the flask was replaced with N₂, weight loss in the PCV and RPV steels, and O₂ and H₂O₂ concentrations in the diluted seawater decreased.     

Effects of gamma-ray irradiation on crevice corrosion repassivation potential of stainless steel in high temperature diluted simulated seawater

The crevice corrosion repassivation potentials (E_R,CREV) of type 304 stainless steel (304 SS) were measured in high temperature (373–553 K), diluted simulated seawater under gamma-ray irradiation, in order to confirm the effects of gamma-ray irradiation on the crevice corrosion behavior of a representative stainless steel in seawater. Overall, for high temperatures, the E_R,CREV values decreased with increasing chloride ion concentration, which was the same as the behavior observed under the non-irradiated condition. The E_R,CREV values measured under gamma-ray irradiation were the same or slightly higher than E_R,CREV values measured under the non-irradiated condition when the [Cl^?] was the same. Consequently, it was confirmed that the threshold potential of crevice corrosion of 304 SS for the gamma-ray irradiation of 1.8 kGy at least did not deteriorate compared with the non-irradiated condition. Under the conditions of this work (seawater composition, [Cl^?] range, dose rate, absorbed dose, flow rate, etc.), the crevice corrosion of 304 SS could be suppressed by maintaining the potential below the threshold potential which was determined approximately as ?0.3 V vs. SHE even for the irradiated condition at temperatures up to 553 K.     

海水泵泵轴腐蚀原因分析及对策

通过浸泡试验和电化学试验对泵轴材料3Cr13的耐蚀性进行了研究。结果表明,3Cr13、镀铬层在海水中不耐局部腐蚀;且3Cr13的自腐蚀电位比其他海水泵部件低,易受电偶腐蚀。综合分析认为导致4号海水泵泵轴腐蚀的根本原因在于泵轴材料3Cr13在海水中不耐局部腐蚀,并在装配间隙、电偶效应等条件的驱动以及泥沙的磨损作用下,发生缝隙腐蚀、电偶腐蚀和磨损腐蚀,加速了泵轴基体的腐蚀进程,从而导致泵轴因腐蚀而失效。建议改进密封和选用耐蚀性更好的替换材料。     

Effects of local radiolysis and geometric parameters on intergranular attack caused by crevice corrosion

Effects of γ-ray irradiation upon crevice corrosion (CC) of type 316L stainless steel (316L SS) as an initiation site of stress corrosion cracking in a boiling water reactor environment have been studied using a material corrosion test loop which could be irradiated with a ⁶⁰Co γ-ray source during testing. The CC tests were conducted using crevice specimens with various sizes of crevice gaps. Many of the examined specimen surfaces exhibited a selective grain boundary dissolution; that is, intergranular attack (IGA) as a result of the CC when the crevice gap size was lower than a certain value. The IGA initiation time was shortened by the γ-ray irradiation. The IGA occurred mostly near the crevice mouth at a distance of less than 2 mm from the mouth edge. When γ-ray exposure had occurred, it was found that the number of IGA sites deeper in the crevice increased compared with the IGA site distribution under the no-irradiation condition. Since the electrochemical corrosion potential inside crevice specimens must be low under the conditions for which IGA could occur, it was assumed that γ-ray irradiation accelerated the corrosion rate of 316L SS by decreasing the Fe²⁺ surface activity inside the crevice or increasing the cathodic current of radiolytic oxidants on the crevice surface. It was concluded that γ-ray irradiation affects the IGA occurrence not only temporally but also spatially.     

甲基苯骈三氮唑和磷酸钠对铜及不锈钢的缓蚀性能研究

针对含铜冷却水系统发生的腐蚀问题,采用电化学测试、浸泡试验及动水试验等方法,研究了缓蚀剂对铜和不锈钢的缓蚀性能和缓蚀机理。结果表明：甲基苯骈三氮唑+磷酸钠复配方案对铜的缓蚀效果最佳,无论纯水还是恶劣水质条件下,缓蚀剂对铜均具有优异的缓蚀作用。同时,缓蚀剂中的磷酸钠提高了不锈钢的击穿电位,因而提高了不锈钢的抗腐蚀性能。     

秦山核电厂海水管道内壁阴极保护系统有效性评价

海水具有较强的腐蚀性,会对以海水为冷却介质的引水和排水管道产生严重的腐蚀.本文通过对秦山核电厂A3钢海水管道腐蚀情况的研究,验证了秦山核电厂海水管道内壁阴极保护系统的有效性,同时积累了原始的腐蚀数据.结果表明,裸露的A3钢在海水中的平均腐蚀速率可达0.35 mm/a,并存在一定程度的孔蚀倾向;秦山核电厂海水管道内壁阴极...     

Effects of seawater components on radiolysis of water at elevated temperature and subsequent integrity of fuel materials

Effects of seawater components on radiolysis of water at elevated temperature have been studied with a radiolysis model and a corrosion test under gamma-ray irradiation conditions to evaluate the subsequent influence on integrity of fuel materials used in an advanced boiling water reactor. In 2011, seawater flowed into the nuclear power plant system of the Hamaoka Nuclear Power Station Reactor No. 5 during the plant shutdown operation. The reactor water temperature was 250 °C and its maximum Cl^? concentration was ca. 450 ppm when seawater was mixed with reactor water. The radiolysis model predicted that the main radiolytic species were hydrogen, oxygen and hydrogen peroxide. Concentrations of radiolytic products originating from Cl^? and other seawater components were found to be rather low. The dominant product among them was ClO₃^? and its concentration was found to be below 0.01 ppm for a 10⁵ s irradiation period. No significant corrosion of zircaloy-2 and 316L stainless steel was found in the corrosion test. These results led to the conclusion that the harmful influence of radiolytic products originating from seawater components on integrity of fuel materials must be smaller than that of Cl^? which is the main ionic species in seawater.     

用背散射X射线穆斯堡尔谱研究涂层下钢铁的腐蚀

用背散射X射线穆斯堡尔谱分析了涂有掺不同颜料的醇酸调合漆的低碳钢在含氯化氢的气氛中的腐蚀产物,以及不同颜料对腐蚀的影响。通过这一实例,表明了背散射X射线穆斯堡尔谱可以成为研究涂层下金属腐蚀的一种有效方法。     

Effect of seawater components on corrosion behavior of SUS316L in nitric acid solution containing metal ions

During the accident that occurred at the Fukushima Daiichi nuclear power plant, a large volume of seawater was introduced as coolant into the storage pools for spent nuclear fuel. If this fuel is reprocessed, some components of seawater will be mixed with the nitric acid solution containing metal ions in the reprocessing process where stainless steels are used as structural material. In this study, we investigated the effect of seawater components in high active liquid waste (HAW) containing nitric acid and metal ions as fission products on the corrosion behavior of SUS316L stainless steel.

Corrosion tests were conducted in surrogate HAW containing artificial seawater (ASW). Intergranular corrosion was observed in the HAW with ASW, where Ru increased the corrosion potential to the transpassive region. An increase in the amount of ASW led to a decrease in the corrosion rate and suppression of intergranular corrosion. Interactions between Ru ions and seawater components, such as chloride ions, were indicated by the results of extended X-ray absorption fine structure spectroscopy and cyclic voltammetry analyses of the solution containing ASW and HAW.     

碳钢对核主泵用奥氏体不锈钢的污染研究

奥氏体不锈钢在加工、运输和装配过程中如果与碳钢直接接触,就会被碳钢污染,而导致奥氏体不锈钢耐蚀性能的改变。众所周知,核主泵用奥氏体不锈钢对耐蚀性有着非常严格的要求,本文以Z2CN18-10核主泵用奥氏体不锈钢为例,通过FeCl3腐蚀试验和电化学方法测试了被碳钢污染后其耐腐蚀性能的变化。试验结果表明:附着在不锈钢表面的碳钢对其长期总体腐蚀速率影响不大;嵌入式的碳钢颗粒会显著降低奥氏体不锈钢的点蚀电位,增大发生点蚀的倾向;硝酸钝化可部分抵消被污染不锈钢点蚀电位的降低,但该值仍远低于同样经过硝酸钝化,而未被污染的不锈钢的点蚀电位。此外,还针对碳钢污染对核电站辐射场的影响和对燃料包壳热传导效率的影响进行了讨论。     

CARR二回路冷却系统碳钢管道的腐蚀与防护

针对中国先进研究堆(CARR)的特殊性,以静态挂片实验与动态模拟实验相结合,采用挂片失重的方法计算腐蚀速率,着重从Cl-、SO2-4、Mg2+和Ca2+浓缩比,pH值,缓蚀阻垢剂浓度等方面开展了碳钢腐蚀影响因素的分析与研究。结果表明,在CARR二回路中,Cl-、SO2-4、Mg2+和Ca2+的浓缩比为2~3,pH值为8.0~8.5,缓释阻垢剂LJ-301的浓度为0.12g/L左右的水质为最佳状态,经24h浸泡或循环水冲击下,20#碳钢的防腐效果明显。     

腐蚀疲劳断裂前氢与缺陷相互作用的正电子湮没研究

用正电子湮没谱和加热释氢研究了低合金高强钢人工海水腐蚀疲劳断裂前经若干小时疲劳的样品。实验结果表明,腐蚀疲劳早期阶段产生的位错、空位团以及钢中晶界是氢的捕获位,其捕获氢量随疲劳时间增加。氢与空位相互作用使空位团尺寸增加,数目增多,氢与位错相互作用促使位错增殖且随疲劳时间增加。晶界与氢相互作用能随疲劳时间、晶界捕获氢量增加而降低。碳化物沿晶析出促进了晶界捕获氢。较低的晶界-氢结合能有利于氢沿晶运动,促使预裂缝沿晶发展。     

Analysis and prevention of corrosion in To chopper systems

T_o neutron choppers at Oak Ridge National Laboratory's Spallation Neutron Source will stop prompt pulses of high-energy neutrons outside the target moderator. Choppers are cooled internally by recirculated distilled water maintained at 15 °C. Numerous metallic components are used to fabricate the choppers and cooling system; water contacts many of these components, establishing a corrosion cell. T_o chopper system corrosion products were investigated analytically. Results showed elevated concentrations of soluble and precipitated iron and copper in cooling water. A chemical-based corrosion strategy was implemented in a T_o chopper system during mechanical tests not involving system irradiation. Chemical analyses showed that a chemical corrosion inhibitor stopped system corrosion for 6 months after its introduction. Corrosion cessation was beneficial, as mechanical tests were performed without interruption from precipitate wear on mechanical parts, flowmeter blockage, or a decrease in heat transfer capabilities. Aqueous chemical changes occurring in the cooling system upon inhibitor addition are discussed.     

注入稀土元素改善钢的耐蚀性

离子注入技术已超出了半导体工业的范围,成为材料科学中强有力的研究手段,并在材料改性领域中开始了工业应用。有人认为离子束技术是进行“材料设计”的手段,是实现“从天然材料到人造材料时代的关键。稀土元素在冶金中的应用很有前途,加入适量稀土可改善钢的机械性能、加工性能和耐蚀性能。但稀土元素改善钢的耐蚀性的作用和机理都有待深入研究,而用离子注入技术系统研究稀土元素改善钢的耐蚀性的工作尚未见报道。我国稀土资源丰富,系统地研究注入稀土元素的作用有重要意义。为了改善航空发动机轴承的抗局部腐蚀性能,美国海军实验室曾将Cr、Mo等常规耐蚀合金元素注入到轴承钢表层,并取得良好效果。本工作亦显示了注入稀土元素改善轴承钢抗点蚀特性的潜力。     

不锈钢堆焊层在Cl-溶液中的腐蚀性能研究

采用浸泡腐蚀试验方法,研究了不锈钢堆焊层材料在Cl^-溶液中的腐蚀情况,并通过金相显微镜、扫描电子显微镜、能谱分析观察表面形貌。研究表明,室温条件下堆焊层材料未发生任何腐蚀。在高温条件下,Cl^-的存在诱导了点腐蚀的发生,且随着Cl^-浓度的增加,点腐蚀加剧;较高浓度的Cl^-可导致缝隙内金属元素Cr的流失,缝隙腐蚀加深;应力腐蚀裂纹有沿晶开裂的特征,应力腐蚀敏感性随Cl^-浓度的增加有提高的趋势。     

Effect of chemical potential of carbon on phase transformation and corrosion of JLF-1 steel in a static lithium

The corrosion and the phase transformation of RAFM (Reduced Activation Ferritic/Martensitic) steel, JLF-1(Fe-9Cr-2W-0.1C), in static lithium (Li) were investigated. The specimens were exposed to static Li at 600 °C for 250 h. The carbon potential in Li was controlled by the carbide formation on inner surface of the crucible, which was made of Mo and Nb. These materials were expected to form stable carbide, and worked as carbon trap in Li, which resulted in the decrease in the carbon potential of Li. The effect of low carbon potential on the corrosion and the phase transformation was characterized by comparison with the test performed in the crucible made of Fe-9Cr and SUS316L (18Cr-12Ni), which has no effect as carbon traps. The low carbon potential caused by Nb and Mo caused the dissolution of carbon from the surface of JLF-1 specimen to Li. The depth of the phase transformation observed after the test in Nb crucible was deeper than that tested in Mo crucible. This was because the stability of the Nb carbide was larger than that of Mo carbide causing larger driving force for the dissolution of carbides from the surface.     

Influence of the chemical composition of austenitic stainless steels on their corrosion behaviour in high-temperature sodium

A contribution to the study of corrosion of stainless steel by high temperature sodium has been made by examining the effect of steel composition. Different types of examination have been made on five different steel samples exposed 1000 h at 700°C. Results of weight losses, carbon analysis and mechanical properties after exposure to sodium as well as argon atmosphere are given. They show that the five steels can be sorted into several families, dependent on their composition. A partial explanation is finally given.     

堆用不锈钢在模拟一回路中腐蚀的穆斯堡尔研究

用透射、内转换电子和内转换X射线发射三种穆斯堡尔谱学方法，配合X射线衍射和俄歇电子能谱研究核电站用不锈钢F316Ti的腐蚀。钝化膜和腐蚀产物的组分及微观结构，提供了研究堆用不锈钢腐蚀的微观结构研究基础。通过腐蚀机理，可以与宏观腐蚀的数据相印证。结果表明，抗蚀不仅与碳含量有关，尤其与热处理过程以及表层固溶状态有关。     

Autogenous healing and reinforcement corrosion of water-penetrated separation cracks in reinforced concrete

Depending on the crack width, the thickness of the structure, the water pressure, and the degree of acid of the water, long-term investigations have been performed over a period of 2 years with respect to the autogenous healing and reinforcement corrosion of water-penetrated separation cracks in reinforced concrete by the University of Kaiserslautern, supported by the Deutsche Forschungsgemeinschaft (DFG). For the waters penetrating the cracks deionised water (neutral, pH=7.0), and boric acid treated deionised water with a pH-value of 6.1 and 5.2 (weakly acid waters) were used. A complete autogenous healing could not be observed. The water penetrating the cracks could hardly be measured with a pH-value of 7.0 at the end of the test. While naturally at the beginning of the test, no influence of the water-chemical degree of the acids could be determined, the existing flow-through quantities towards the end of the test period depended clearly on the crack width and the pH-value. With an increasing crack width and an increasing acid-degree larger flow-through quantities were measured. Depending on the pH-value and the crack width it was determined whether and to which extent corrosion developed at the reinforcing steel bars crossing the cracks. With a crack width of 0.1 mm, corrosion was not to be observed in any case. For the test specimens with a crack width of 0.2 mm a start of the corrosion was found depending on the pH-value. With an increasing width of the crack, an increasing corrosion development is to be expected for test specimens penetrated by acid water. For a crack width of 0.4 mm and a pH-value of 5.2, the highest corrosion development was to be observed, however, there were weakenings of the cross section not worth being mentioned even after a 2-year test period.