Modeling microbial sulfate reduction and the consequences for corrosion of copper canisters

The copper sulfide model (CSM) is a one-dimensional reactive transport code for predicting the evolution of the corrosion behavior of a copper canister in a deep geological repository. Here, the CSM has been extended to simulate the microbial reduction of sulfate in the repository and the consequences for corrosion of the canister. Organotrophic and chemotrophic sulfate reduction are represented by Monod kinetics, along with the dissolution of solid organic matter and gypsum as sources of nutrient and an electron acceptor, respectively. Siderite dissolution in the buffer and tunnel backfill materials acts as a source of Fe(II), which can then precipitate the microbially produced sulfide as mackinawite. Results are presented for a simulation representing the expected evolution of the corrosion behavior and repository environment and for a series of sensitivity analyses designed to identify the most important processes in the overall reaction scheme.     

General and localized corrosion of magnesium alloys: A critical review

Magnesium (Mg) alloys as well as experimental alloys are emerging as light structural materials for current, new, and innovative applications. This paper describes the influence of the alloying elements and the different casting processes on the microstructure and performance of these alloys and corrosion. It gives a comprehensible approach for the resistance of these alloys to general, localized and metallurgically influenced corrosion, which are the main challenges for their use. Exposure to humid air with ∼65% relative humidity during 4 days gives 100–150 nm thickness. The film is amorphous and has an oxidation rate less than 0.01 μm/y. The pH values between 8.5 and 11.5 correspond to a relatively protective oxide or hydroxide film; however above 11.5 a passive stable layer is observed. The poor corrosion resistance of many Mg alloys can be due to the internal galvanic corrosion caused by second phases or impurities. Agitation or any other means of destroying or preventing the formation of a protective film leads to increasing corrosion kinetics. The pH changes during pitting corrosion can come from two different reduction reactions: reduction of dissolved oxygen (O) and that of hydrogen (H) ions. Filiform corrosion was observed in the uncoated AZ31, while general corrosion mainly occurred in some deposition coated alloys. Crevice corrosion can probably be initiated due to the hydrolysis reaction. Exfoliation can be considered as a type of intergranular attack, and this is observed in unalloyed Mg above a critical chloride concentration.     

Formation of oxides on copper in alkaline solution and their photoelectrochemical properties

The anodic formation of Cu(I) and Cu(II) oxides on polycrystalline copper in a deaerated alkaline solution is studied using the technique of the synchronous recording of transients of the photocurrent and polarization current. The oxide formation in a currentless mode is analyzed via the synchronous recording of photopotential and corrosion potential. It is found that copper is susceptible to corrosion oxidation due to traces of dissolved oxygen with the formation of a Cu(I) oxide. The preliminary formation of the underlayer of anodic Cu(I) oxide on copper hinders its further corrosion oxidation. It is confirmed that copper oxides Cu₂O and CuO, which appear on copper in both anodic and corrosion modes of formation, are p-type semiconductors. The initial stage of anodic oxidation of copper is characterized by the formation of an intermediate compound of Cu(I), possibly CuOH, which exhibits n-type conductivity. A film of Cu(I) oxide is thin and has a band gap of 2.2 eV for indirect optical transitions. Anodic polarization in the range of potentials of CuO formation leads to the formation of a thicker oxide film, which is a mixture of Cu(I) and Cu(II) oxides.     

铜铬合金在二氧化硫环境中的腐蚀行为

采用SEM、XPS等测试方法,研究了铜铬合金在二氧化硫环境中的腐蚀情况。结果表明,铜铬合金的耐蚀性较纯铜的耐蚀性有一定程度的提高;XPS分析显示,当合金试样在腐蚀环境中的增重量不再随时间发生变化时,合金表面的腐蚀产物以铜的硫酸盐为主,腐蚀产物中没有发现含Cr相的存在;另一方面,由于合金中低含量的Cr不能在试样表面独立成膜,所以合金耐蚀性的提高很大程度上依赖于致密腐蚀产物层对合金基体的保护作用。     

Electrochemical noise from oxygen reduction on stainless steel surfaces

Oxygen reduction occurring at the passive layer is probably the most important cathodic reaction involved in corrosion processes on stainless steel. Furthermore, the influence of the surface state on the oxygen reduction reaction is a key point for the understanding of the mechanism of localized corrosion on stainless steel. In this study, electrochemical noise measurements under cathodic polarization were carried out to obtain new information about this influence. It has been confirmed that the surface state of stainless steel plays a very important role in the kinetic of this cathodic reaction. Oxygen reduction kinetics was significantly reduced on passivated surfaces and improved on pre-reduced and ground surfaces. In addition, electrochemical current noise measurements allowed to differentiate between the electrochemical activity produced by the oxygen reduction reaction and that due to the reduction of the passive layer, in direct dependence on the characteristics of the different surface states investigated.     

无氧铜表面特定清洗液的腐蚀机制及溶液特性

目的通过无氧铜特定清洗液的溶液配方实验、腐蚀机制测定以及清洗液浓度表征,为实现无氧铜稳定清洗提出技术方案。方法采用铬酐和浓硫酸互配进行溶液配方实验并采用扫描电镜形貌和腐蚀速率对结果进行对比分析;采用电化学循环伏安法研究了铜浓度对腐蚀速率的影响;采用EDTA络合滴定法测定铜浓度和氧化还原滴定法测定六价铬浓度进行了分析。结果 60~80 g/L铬酐+40~60 m L/L硫酸+余量水的溶液清洗可以获得均一稳定的表面,其中铬酐发挥着氧化剂的作用,硫酸发挥着调整酸度的作用;适当的铜离子浓度对化学反应有促进作用,随着铜离子质量浓度增大至5 g/L以上,腐蚀动力减缓,腐蚀速率减慢。结论提出了无氧铜稳定清洗的合适浓度,得出了腐蚀机制及溶液特性的具体结果。     

Corrosion protection properties of copper‐ and carbon‐containing polyethylene films in humid air climates

The corrosion protection properties of commercially available polyethylene (PE) films containing copper and carbon were investigated and compared with pure PE films of comparable thickness. The composition of these films was analyzed by thermoanalysis and atom emission spectroscopy (ICP‐AES). Electrochemical impedance spectroscopy (EIS) and packaging tests were used to determine the ability of copper‐ and carbon‐containing PE films to protect mild steel against corrosion in humid air climates. For the here‐investigated samples, no electrochemical activity of copper could be found under these conditions. In contrast to the added copper only the inserted carbon decreased the surface resistance. Additional abrasive tests imply that copper is encapsulated inside the films. For all samples, the permeability to vapor and the insertion of water were similar to the copper and carbon free reference film. The tests in the climate cabinet revealed that mild steel samples packed in copper‐ and carbon‐containing films reached the same degree of corrosion than those in the reference films.     

Korrosionsschäden an Bronzeplastiken

Corrosion damage of bronze sculptures In order to assess the effect of contaminated air (industrial and urban atmospheres) on bronze sculptures the composition of the base metal and of the corrosion products has been investigated pn a number of sculptures in the open air. in addition to the corrosion products typical of bronze — basic copper sulfate, basic copper nitrate, basic copper chloride stannous acid, lead sulfate — other compounds have been found which — as e.g. gypsum — are formed by reaction between dust and atmospheric contaminats. The corrosion layers usually include several strata; soot containing strata are characteristic of the winter season. Oils, waxes and plastic coating are suitable agents for protecting bronze sculptures against corrosion. The two first mentioned materials are suitable in particular for older bronzes having a natural or artificial patina; they require, however, renewal after regular intervals; plastic coatings are suitable for application to bright metal surfaces and are more durable. Despite the high manpower requirement it is advisable regularly to clean the sculptures with detergent containing water.     

Corrosion inhibition of copper in chloride media by 1,5-bis(4-dithiocarboxylate-1-dodecyl-5-hydroxy-3-methylpyrazolyl)pentane

The efficiency of 1,5-bis(4-dithiocarboxylate-1-dodecyl-5-hydroxy-3-methyl-pyrazolyl)pentane (BDTCPP) as copper corrosion inhibitor in 3.5% NaCl solutions was studied by electrochemical polarization methods (Tafel extrapolation and polarization resistance method), electrochemical impedance spectroscopy and immersion assays. Results obtained in this study reveal that BDTCPP is a good inhibitor and the potentiodynamic polarization studies clearly show that BDTCPP is a mixed-type inhibitor for copper in chloride solutions. It decreases the anodic reaction rate more strongly than the cathodic reaction rate and it renders the open circuit potential of copper more positive in 3.5% NaCl solutions. The UV analysis of the protective layer of BDTCPP after corrosion experiments shows that the inhibitor prevents copper corrosion by physisorption on the metal surface, followed by chemisorption of a protective Cu(II)-complex. This Cu(II) is generated by oxidation of the Cu(I) ion formed at the beginning of the corrosion process in the aerated solution of NaCl.     

Piezoelectric Microbalance and its use in the Study of Volatile Inhibitors

Abstract

The principle of the piezoelectric microbalance is described and its applicability to the surface reaction studies on metals is discussed. The adsorption of cyclohexylamine o-nitrophenolate on copper and silver and its protective action against corrosion in humid air were studied using the piezoelectric micro-balance. The results of measurements are given as an example of the application of the method in corrosion and inhibition research. Finally, advantages and limitations of the method are briefly discussed.     

Influence of Deteriorated Bentonite Sediments on the Corrosion Behavior of NiCu Low Alloy Steel

The corrosion evolution of steel disposal container largely depends on the evolution of surrounding bentonite environment in the long-term geological disposal of high-level radioactive wastes. This study focused on the influence of the deteriorated bentonite sediments on the corrosion behavior of NiCu low alloy steel in the top supernatant and bottom slurry formed by Gaomiaozi bentonite and 0.05 M NaHCO₃ + 0.1 M NaCl + 0.1 M Na₂SO₄ solution. In the top supernatant, the cathodic process of the steel corrosion was transformed from the reduction in oxygen to the reduction in ferric corrosion products with time as same as that in the blank solution. While in the bottom bentonite slurry, the cathodic process always maintained as the hydrogen evolution reaction due to the coverage of more bentonite sediments. Meanwhile, the corrosion rate of NiCu steel was obviously decreased. In addition, the localized corrosion tendency of the steel could also be reduced by the large amount of deteriorated bentonite sediments.     

Corrosion products of tin in humid air containing sulfur dioxide and nitrogen dioxide at room temperature

To obtain a fundamental understanding of the corrosion behavior of tin in corrosive gas environments, in situ infrared reflection absorption spectroscopy measurements were carried out on tin in humid air containing SO₂ and NO₂ at room temperature. A series of time-resolved in situ IR spectra in air of 90% relative humidity (RH) containing 10-22 ppm SO₂ suggested that the oxide films on tin specimens had a protective effect and that no significant corrosion occurred. The corrosion products in air of 80-90% RH containing 10-22 ppm NO₂ were SnO₂, SnO, nitrate and hyponitrite. The synergistic effect of SO₂ and NO₂ on corrosion of tin was not observed in humid air (RH of 90%) containing 0.84 ppm SO₂ and 1.8 ppm NO₂.     

稠油热采管BG90H钢在不同条件下的腐蚀行为

通过干空气和湿空气以及在H_2S和CO_2共存条件下腐蚀试验模拟油田现场稠油热采的过程,研究了稠油热采管BG90H钢在不同条件下的腐蚀行为。结果表明:BG90H钢在干空气中的均匀腐蚀速率小于在湿空气中的均匀腐蚀速率,在湿空气中材料出现局部腐蚀(点蚀);湿空气中水蒸气含量大,在金属材料表面结露、均匀成膜,且供氧充分,使BG90H钢的吸氧腐蚀速率显著上升,由于完整液膜下试样表面腐蚀原电池数量的显著增多,材料点蚀程度显著增强。在CO_2和H_2S共存腐蚀条件下,腐蚀速率在120℃出现最大值,此时金属表面上生成一层疏松的、多孔且较厚的腐蚀产物膜;当温度在100~120℃及大于180℃时,局部腐蚀较为严重,但在150~180℃时,局部腐蚀轻微;腐蚀过程由CO_2/H_2S联合交替控制。     

Quantitative determination of corrosion products and adsorbed water on copper in humid air containing SO2 by IR-RAS measurements

The time dependency of the amounts of corrosion products and co-existing adsorbed water on copper in humid air containing SO₂ was estimated from a series of in situ time-resolved IR-RAS spectra on the basis of the relations between the band intensities and the mass changes of the corrosion products, which were determined by simultaneous measurement of IR-RAS and QCM. The amounts of both corrosion products increased slowly at the initial stage and later increased rapidly. Although the relative humidity was kept constant, the amount of adsorbed water increased nearly the same behavior as that of corrosion products in the stage of relatively small amounts of corrosion products and later increased rapidly when the amounts of corrosion products increased. In humid air without SO₂, sulfite gradually decomposed and some of it changed into sulfate.     

Characterisation of reaction layers on copper surfaces formed in aqueous chloride and sulphate ion containing electrolytes

Copper is in a passive state in a potential range of 50 mV_H to about 300 mV_H in contact with an aqueous electrolyte at neutral pH caused by the formation of a thin tarnishing layer consisting of copper(I)-corrosion products. This layer inhibits more the anodic than the cathodic partial reaction of the corrosion process. The steep threshold in the transpassive range leads to the oxidation of copper and the formation of secondarily formed reaction layers. In sulphate containing electrolytes voluminous reaction layers of crystalline non-protective copper(I)-oxide are formed. The manifestation of corrosion is general attack. In chloride containing electrolytes a two-fold reaction layer is formed, copper(I)-chloride underneath copper(I)-oxide. This amorphous copper(I)-oxide is formed via hydrolysis of copper(I)-chloride and inhibits anodic metal dissolution. The only observed manifestation of corrosion is repassivating pitting.     

Corrosion of aluminium in copper-aluminium couples under a marine environment: Influence of polyaniline deposited onto copper

In this study, we examined how aluminium corrosion in Al-Cu/PANI galvanic couples in a marine environment is influenced by deposition of polyaniline (PANI) on copper. Polarization curves and immersion assays in 0.1 M NaCl were performed. The morphologies of etched Al and corrosion products were observed by SEM, and the Al ions in solution were quantified by atomic absorption spectroscopy. A reduction in aluminium damage due to galvanic corrosion was observed as a result of decreased effective area for the oxygen reduction reaction on Cu/PANI electrode. Furthermore, an electrochemical reduction of PANI from leucoemeraldine to emeraldine base is proposed.     

Long-Term Behaviors of Oxide Layer in Liquid Lead–Bismuth Eutectic (LBE), Part II: Model Applications

This article is Part II of the systematic study on the long-term behaviors of the protective oxide layer in liquid lead–bismuth eutectic (LBE) systems. The model developed in Part I is applied to analyze the kinetics of the growth of the oxide layer formed on cladding materials (HT-9 and T-91 steel) of an LBE-cooled small modular reactor. It is found that the outer magnetite layer of initially formed duplex-layer oxide structure on cladding steels can be completely removed in a long-term operation through chemical reaction with the liquid metal and mass transfer by the liquid metal flow, which causes the inner compact spinel layer to contact with LBE directly. The present calculations indicate that the corrosion rate of the steels considered is reduced by approximately three orders of magnitude after the magnetite layer is removed. Increasing the velocity of the LBE flow can reduce the time needed for removal of the magnetite layer, which benefits the steel corrosion resistance for a long-term operation. The oxide layer properties and growth kinetics are also analyzed. The operation ranges of the flow velocity and the oxygen concentration are developed based on the modeling results, which indicates both T-91 and HT-9 have appropriate corrosion resistance and can be applied as cladding materials for a 10-year operation if the oxygen concentration is well controlled.     

血清白蛋白对模拟宫腔液中铜腐蚀的影响

为研究含铜宫内节育器的铜离子释放行为,在体外试验条件下考察了宫腔液中添加生化组份人血清白蛋白对铜腐蚀行为的影响。极化电阻测试的结果表明,在所研究的ＰＨ和氧分坟范围内,白蛋白总是使铜的腐蚀速度相对于无白蛋白的情况有所增大同时发现,中性条件下当白蛋白的浓度较小时,铜的腐蚀速度随白蛋白浓度的增大而增大;当白蛋白浓度大时,铜的腐蚀速度随白蛋白浓度的增大反而有所减小并趋势于一稳定值。腐蚀试验后铜试样表面ＸＲ     

Corrosion of metals in wood: Comparing the results of a rapid test method with long-term exposure tests across six wood treatments

This paper compares two methods of measuring the corrosion of steel and galvanized steel in wood: a long-term exposure test in solid wood and a rapid test method where fasteners are electrochemically polarized in extracts of wood treated with six different treatments. For traditional wood preservatives, the electrochemical extract method correlates with solid wood exposure which suggests that the reduction of cupric ions is the cathodic reaction in both the solid wood and the extract. For treatments without copper, the extract method predicted a higher corrosion rate than the solid wood exposure. For these treatments, the cathodic reaction appears to be the reduction of acid and dissolved oxygen. The practical implication of this work is that in some cases, the rapid test method could be used to screen new fasteners and wood preservatives. Scientifically, this work increases the understanding of the mechanism of corrosion of fasteners in treated and untreated wood.     

A correlation between electrochemical behaviour, composition and semiconducting properties of naturally grown oxide films on copper

Copper(I) oxide films formed under open-circuit potential in neutral aqueous solutions have been characterized, using coulometry, photocurrent spectroscopy and X-ray photo-electron spectroscopy (XPS). The reduction potential of the oxide layer was found to depend on the presence in the electrolyte of chloride ions, Cu(II) or Cu(I) ionic species or of a corrosion inhibitor. XPS analyses were performed on these oxide layers, and showed in some cases an evolution of the oxidation state of copper from + 2 to + 1 state throughout the film. Different conducting properties of the cuprous oxides could be demonstrated through photo-electrochemical measurements, and the formation of a duplex Cu₂O layer with two semiconducting components of different stoichiometries was discussed.