The corrosion of mild and stainless steel in alkaline anaerobic conditions representing the Belgian “supercontainer” concept and the Swiss L/ILW repository

Deep geological repositories for radioactive waste contain metallic materials, either used to construct disposal canisters or as low-/intermediate-level waste (L/ILW). The safety relevance of corrosion is linked to canister lifetime in the former case and gas generation in the latter. More specifically, the Belgian “supercontainer” concept envisages mild steel for the used fuel disposal canister, and in the case of the Swiss L/ILW repository, mild steels are the largest metallic waste component due to the decommissioning of civilian power-generating facilities. For these circumstances, the corrosion environment is dominated by the chemistry of cement, which is used as buffer or backfill material. The corrosion behaviour of mild steel in anoxic environments was studied through the analysis of the hydrogen end-product. Hydrogen analysis was conducted by periodically purging the cell head-space and analysing the gas using a solid-state hydrogen sensor. While this method is limited to providing only uniform corrosion rates averaged over periods of time, ranging from weeks to months, it provides excellent resolution and sensitivity. The test cell environments were matched against the anticipated Belgian high-level waste and Swiss L/ILW repository environments, and also against experiments that have been conducted by other researchers for comparative purposes. Samples were exposed to synthetic cement pore waters, representing fresh and degraded cement. In young cement waters, the formation of initial corrosion products resulted in steel wire corrosion rates of the order of µm/year, which, at 80°C rapidly declined to ∼10 nm/year. In contrast, SA516 grade 70 steel plate corroded much more slowly under similar conditions. In aged cement waters, initial corrosion rates were higher but declined faster towards a longer-term rate of ∼10 nm/year. 316L stainless steel, embedded in cementitious material, corroded at a rate of <1 nm/year at 50°C.     

Effect of temperature on copper corrosion in high-level nuclear waste environment

The effect of temperature on the corrosion behavior of copper in simulated high-level nuclear waste environment was systematically studied. Electrochemical methods, including electrochemical impendence spectra, Mott–Schottky technology, cyclic polarization, and potentiostatic polarization, were employed to characterize the corrosion behavior of copper at different temperatures. Stereoscopic microscopy and scanning electron microscopy were used to examine the surface morphology, and X-ray photoelectron spectroscopy analysis was used to identify the composition of the passive film. The experimental results show that corrosion resistance of the passive film does not blindly decrease with the increase of temperature but increases at 60 °C owing to a compact outer layer; there is a potential for pitting corrosion, which decreases as the temperature increases. The main product of copper in an anaerobic aqueous sulfide solution is Cu₂S but the content of CuS increases at higher temperatures. The whole passivation range shows p-type semiconductor characteristics and the magnitude of the acceptor density is 10²³ cm^?3, which increases with increasing temperature.     

Sulphide-induced stress corrosion cracking and hydrogen absorption of copper in deoxygenated water at 90°C

Stress corrosion cracking (SCC) of oxygen-free phosphorous-alloyed copper was investigated in sulphide- and chloride-containing deoxygenated water at 90°C with sulphide concentrations of 0.001 and 0.00001 M. Several intergranular defects were found in the specimen exposed to the high sulphide environment. Similar defects were not found in the low sulphide environment, where only slight corrosion on grain boundaries and slip lines occurred. Hydrogen content measurements show an increase in hydrogen uptake of the plastically deformed specimens, which is dependent on the sulphide concentration and on plastic deformation of copper. However, the highest hydrogen content was measured in friction stir welds, welded in air without shielding gas, and tested in the high sulphide environment. The embedded oxide particles in the weld metal act as local hydrogen trapping sites and selectively react with the sulphide solution. A relatively thick air-formed oxide film covers the copper canisters when deposited, which transforms into a sulphide film in the repository conditions. Thus, some of the coupon specimens were pre-oxidised. The conversion of the pre-existing Cu₂O film into Cu₂S film occurs quickly and the transformation is almost 100% efficient. The structure and properties of the Cu₂S films, susceptibility of copper to sulphide-induced SCC and hydrogen uptake of copper in reducing, anoxic repository conditions are discussed.     

锅炉水冷壁管开裂原因分析

针对某火电厂锅炉水冷壁管开裂情况,通过宏观形貌、材质分析、硬度检测、显微组织检测、扫描电镜、能谱分析和XRD等手段,对水冷壁开裂管进行取样分析。结果表明水冷壁管开裂的原因是氢腐蚀;主裂纹内部和氧化层缝隙存在大量铜,氧化层导热性能差,恶化局部传热,局部热负荷超过一定极限时,大大加速铜在主裂纹处富集,富集的铜元素又加速了裂纹的扩展。     

氢对铜的电化学行为和应力腐蚀的影响

纯铜充氢后并不改变组织结构和晶粒大小而且抗拉强度、伸长率和面缩率也不变化，这表明铜没有氢脆，在ＮａＮＯ＿２溶液中，氢使纯铜电位降低，使应力腐蚀开裂敏感性升高，但断口形貌不发生变化。     

Corrosion domain analysis of copper corrosion in aqueous media

Abstract

The technology that is being developed in Sweden for the disposal of high level nuclear waste calls for storage of the waste in copper canisters, which are encapsulated in a bentonite buffer contained in drill holes in the floors of drifts (tunnels) in a granitic rock repository. A controversial issue has arisen during the development of this technology: that copper, when in contact with pure water under anoxic conditions corrodes and hence is not immune as previously believed. This issue is resolved in the present paper by deriving corrosion domain diagrams as a means of presenting the thermodynamics of the system in the clearest form possible, when assessing the immunity and activation of copper.     

Corrosion of copper-coated used nuclear fuel containers due to oxygen trapped in a Canadian deep geological repository

The Nuclear Waste Management Organization is evaluating the safety and feasibility of the permanent disposal of used nuclear fuel in a deep geological repository. Their current design concept utilises copper-coated steel used fuel containers to isolate the waste from the environment. Immediately following repository closure, a finite quantity of O₂ will be trapped inside the repository and could cause some amount of oxic corrosion to the outer copper layer of the containers. On a per container basis, 13?mol of O₂ will be trapped in the repository rooms at the time of closure, based on reference design dimensions. This corresponds to a maximum depth of copper corrosion of 81?μm, assuming a uniform distribution. This work also considers the sensitivity of this oxic corrosion allowance to various hypothetical design changes to the repository that may occur before or during construction.     

Reaction of native copper in contact with pyrite and bentonite in anaerobic water at elevated temperature

Copper pellets were reacted with different solutions, reference minerals, and well-characterised bentonites to investigate the effect of different bentonites on the stability of native copper in repository concepts for high-level radioactive waste. The reaction of Cu in contact with bentonite used as barrier material to store high-level radioactive waste was significantly affected by the presence of sulphides (e.g. pyrite) leading to a specific corrosion. Bentonites free of pyrite are not actively involved in a reaction with Cu. Nevertheless, slightly different Cu mass losses were found for different bentonites. For different bentonites, different coatings were found on the Cu surface. The characteristics of these coatings are probably responsible for different Cu mass losses of Cu in contact with different bentonites. As an example, particularly dense coatings led to a decrease in Cu mass loss. No relation of the Fe-corrosivity of different bentonites with Cu mass loss was found, which proves that the Fe-corrosion mechanism differs from the Cu-corrosion at the metal/bentonite interface. The experiments also demonstrated the importance of the presence even of traces of oxygen.     

国产核级E308L焊条在高温水环境下均匀腐蚀行为

结合腐蚀增重和腐蚀失重变化并利用SEM、XRD和XPS等手段,研究了国产核级E308L不锈钢焊条熔敷金属在模拟核电一回路水环境中的均匀腐蚀性能。结果显示,随着腐蚀周期的增加,腐蚀增重和腐蚀失重均为先迅速增加,随后增加趋缓,而试样表面氧化物颗粒数量和尺寸逐渐增大,氧化膜的主要成分为Fe和Cr的氧化物。3000 h内国产核级E308L不锈钢焊条具有良好的抗均匀腐蚀性能。     

腐蚀监控技术在炼油装置中的应用

随着原油品质的下降,在炼油过程中造成的腐蚀问题,受到广泛重视,腐蚀监控技术得到快速发展.炼油装置中的均匀腐蚀情况可以通过电阻探针监控法和电感探针监控法来进行监控,点腐蚀情况可以通过线性极化探针监测法和电化学噪声监控技术来进行监控,应力腐蚀情况可以通过氢通量测量技术和线性极化探针监控法来进行监控.基于这些腐蚀监控技术,建...