A new perspective on measuring the corrosion rate of localized corrosion

Many corrosion phenomena are nonuniform, which means that anodic and cathodic locations are spatially separated. An example is macrocell corrosion of steel in concrete. Under these conditions, determining the corrosion rate from polarization resistance measurements and using the Stern–Geary equation is fundamentally not possible. We present a novel theoretical approach for the interpretation of galvanostatic pulse measurements, to make them applicable as a method for corrosion rate measurements in situations of localized corrosion. Experiments show that it is important to consider that (a) only a fraction of the applied current flows through the anode of the macrocell, and (b) this current is not constant over time. We propose an approach to quantify and consider these two effects, based on information generally accessible in condition assessment of concrete structures. Our results show that galvanostatic pulse measurements are a robust method to determine the corrosion current. With the traditional empirical approach, the measurement error was generally below factor 3, and occasionally up to factor 10. With the novel approach, this error could be reduced to a factor of maximum 2 in all cases.     

Initial atmospheric corrosion of Zinc sprayed with NaCl

1　INTRODUCTIONAsamainacceleratorofatmosphericcorrosionofmetalsinmarineenvironments ,sodiumchloride ,Na Cl,canabsorbwatervaporfromhumidairtoformthinwaterfilmonthemetalsurface .Theroleofthiswaterlayeristoprovideamediumformobilizationofions.NaCldissolvedinthelayeralsoconsiderablyraisestheconductivityoftheelectrolyte .Thiswillgreatlyincreasetheelectrochemicalcorrosionandaf fectthecompositionofthecorrosionproducts .ItisthereforeofgreatinteresttostudytheeffectofNaClontheatmosphericcorrosiono…     

A practical method for calculating the corrosion rate of uniformly depassivated reinforcing bars in concrete

The quantification of active corrosion rate of steel in concrete structures through nondestructive methods is a crucial task for scheduling maintenance/repair operations and for achieving accurate service life predictions. Measuring the polarization resistance of corroding systems and using the Stern‐Geary equation to calculate the corrosion current density of active steel is a widely‐used method for this purpose. However, these measurements are greatly influenced by environmental factors; therefore, accurate monitoring of corrosion requires integrating the instantaneous corrosion rates over time. Although advanced numerical models are helpful in research settings, they remain to be computationally expensive and complex to be adopted by general engineering community. In this paper, a practical numerical model for predicting corrosion rate of uniformly depassivated steel in concrete is developed. The model is built on Stern's earlier work that an optimum anode‐to‐cathode ratio exists for which the corrosion current on the metal surface reaches a maximum value. The developed model, which represents the corrosion rate as a function of concrete resistivity and oxygen concentration, is validated using experimental data obtained from the literature.     

基于动态杂散电流和二氧化碳干扰的输气管道表面腐蚀速率研究

目的预测输气金属管道表面腐蚀速率。方法分析动态杂散电流和二氧化碳(CO_2)浓度对金属管道的表面腐蚀机理,给出金属管道表面腐蚀产生的化学反应方程式。根据一元回归线性方程式得出多元线性回归数学方程式,推导出动态杂散电流和CO_2腐蚀金属管道表面方程式,得出金属管道表面腐蚀预测的最终模型。结合具体实例,采用数学软件MATLAB对45号金属管道表面腐蚀速率预测的多元线性回归模型进行仿真,并且与实验测量的腐蚀速率进行比较和分析。结果金属管道表面的腐蚀速率随着动态杂散电流或者CO_2浓度的增大而逐渐增大。在100 h内,电流和CO_2浓度仿真的金属管道表面最大腐蚀速率分别为3.72×10~(–4) mm/h和4.80×10~(–4) mm/h,电流和CO_2浓度仿真的金属管道表面最小腐蚀速率分别为3.26×10~(–4)mm/h和4.24×10~(–4) mm/h,电流和CO_2浓度实验测量的金属管道表面最大腐蚀速率分别为3.76×10~(–4) mm/h和4.86×10~(–4) mm/h,电流和CO_2浓度实验测量的金属管道表面最小腐蚀速率分别为3.12×10~(–4) mm/h和4.08×10~(–4)mm/h。同时,金属管道表面腐蚀速率理论计算值与实验测量值的相对误差在5%以内。结论采用多元线性回归模型可以近似预测输气金属管道表面的腐蚀速率,为管道的使用寿命提供参考数据,避免输气金属管道发生重大安全事故。     

Long-term atmospheric corrosion of zinc

A great deal of information is available on the short- and mid-term atmospheric corrosion of zinc: corrosion rate data as a function of atmosphere type, corrosion mechanisms, effect of environmental variables, effect of surface orientation, damage functions, etc. However, very little information has been published on the atmospheric corrosion of zinc over long time periods (10-20 years), despite its great usefulness. On the other hand, many studies have analyzed the nature of corrosion products formed on zinc in a wide range of atmospheric environments, using different experimental techniques, but few have focused on the morphology of corrosion product layers. This paper reports the characteristics—mainly composition and morphology—of corrosion products formed on zinc panels after long-term exposure (13-16 years) in various types of atmospheres in Spain: rural, urban, industrial, mild marine and severe marine.     

A mathematical model for prediction of time from corrosion initiation to corrosion cracking in RC structures

Prediction of time from corrosion initiation to corrosion cracking is a crucial factor in evaluating concrete structures' durability and integrity deteriorated by reinforcement corrosion. This paper presents a mathematical model to predict the time from corrosion initiation to corrosion cracking. A dynamic corrosion rate model based on Bulter–Volmer kinetics and a rust expansion model based on Faraday's law are developed. An analytical model is developed to demonstrate the mechanical consequences of rust buildup around the rebar. The time to corrosion cracking is found to be a function of surrounding concrete material properties, chemical composition of rust, ratio of concrete cover thickness to rebar diameter, and corrosion current density. Comparisons with available experimental results are conducted to show the accuracy and reliability of the present model. Further parametric analysis is carried out to show the influences of various parameters included in the model on the time to corrosion cracking.     

Atmospheric corrosion of zinc induced by runoff

Atmospheric corrosion and runoff of zinc were investigated during two years in humid tropical climate on hot dip galvanized steel and zinc samples. The high zinc mass loss (14.70 g m⁻²) is induced by the intensive zinc release (12.40 g m⁻²). No corrosion phase containing chloride was detected on the zinc surface, while a variety of sulfates not dissolved by rains reveals the sensitivity of zinc to SO₂ pollutant. However, two chloride-containing corrosion products were detected on the galvanized steel. Exponential equation is proposed that fits well the experimental data for zinc mass loss induced by runoff process as a function of the time of wetness. The formula gives possibility to predict the mass loss even before a steady state in the corrosion process has been reached. This equation can converge to a Benarie lineal function (C = At_w), when the coefficient b = 1 for the corrosion which is accelerated with the partial removal of the corrosion layer during the runoff phenomena.     

Markov chain modelling of pitting corrosion in underground pipelines

A continuous-time, non-homogenous linear growth (pure birth) Markov process has been used to model external pitting corrosion in underground pipelines. The closed form solution of Kolmogorov’s forward equations for this type of Markov process is used to describe the transition probability function in a discrete pit depth space. The identification of the transition probability function can be achieved by correlating the stochastic pit depth mean with the deterministic mean obtained experimentally. Monte-Carlo simulations previously reported have been used to predict the time evolution of the mean value of the pit depth distribution for different soil textural classes. The simulated distributions have been used to create an empirical Markov chain-based stochastic model for predicting the evolution of pitting corrosion depth and rate distributions from the observed properties of the soil. The proposed model has also been applied to pitting corrosion data from pipeline repeated in-line inspections and laboratory immersion experiments.     

Potential and current distributions of one-dimensional galvanic corrosion systems

Many practical galvanic corrosion problems can be simplified into a one-dimensional mathematical equation. In this study, theoretical expressions for galvanic potentials and currents of one-dimensional systems are deduced and some critical parameters involved in the potential and current equations are systematically discussed. The developed analytical approach is then applied to some practical galvanic corrosion cases, such as a steel-Al joint exposed to bio-fuel E85, a galvanic couple separated by a passive spacer and a scratched organic coating. It is demonstrated that the analytical approach can examine the reliability of a computer modeled galvanic corrosion process and help understand the mechanism behind the computer modeled galvanic corrosion behavior.     

Theoretical considerations on the supposed linear relationship between concrete resistivity and corrosion rate of steel reinforcement

Traditionally, the assessment of service life of steel reinforced concrete structures has been focused on the prediction of the time required to achieve a transition from passive to active corrosion rather than to accurately estimate the subsequent corrosion rates. However, the propagation period, i.e. the time during which the reinforcing steel is actively corroding, may add significantly to the service life. Consequently, ignoring the propagation period may prove to be a conservative approach. On the other hand the prediction of the corrosion rate may result in a very complex task in view of the electrochemical nature of corrosion and the numerous parameters involved. In order to account for the various influences an essentially empirical model has been introduced in which the electrolytic resistivity of the concrete environment serves as the major parameter. This model will be discussed for carbonation‐induced corrosion based on the commonly accepted theory of aqueous corrosion. An alternative model for microcell corrosion is proposed which is based on the commonly accepted view that anodic and cathodic sites are microscopic and their locations change randomly with time. In line with this view electrolytic resistivity can be incorporated and thus may play a significant role in the kinetics of the corrosion process. For a wide range of corrosion current densities the relationship between corrosion current density, log(i_corr), and concrete resistance, log(R_con), can then be approximated by an almost ideal linear relationship. Assuming a fixed geometrical arrangement of anodic and cathodic sites on the steel surface, this linear relationship is also valid for concrete resistivity, ρ_con. However, from the theoretical treatment of the electrochemical processes underlying reinforcement corrosion it becomes evident that a linear relationship between corrosion current density and concrete resistivity does not necessarily imply that concrete resistance is dominating the overall corrosion cell resistance. In most cases a significant portion of the driving voltage of the corrosion cell will be consumed by the transfer of electrical charge involved in cathodic reactions, i.e. cathodic activation control will dominate.     

Initial corrosion behavior of pure zinc in simulated tropical marine atmosphere

The initial corrosion behavior of pure zinc in a simulated tropical marine atmosphere was investigated using gravimetric method, scanning electron microscope combined with energy dispersive spectroscopy (SEM-EDS), X-ray diffractometry (XRD), Fourier transform infrared spectrometry (FTIR) and electrochemical impedance spectroscopy (EIS). The kinetics of corrosion process is a decelerating process following the empirical equation D=Atⁿ (n<1). The protectiveness of the corrosion product layer could be attributed to the formation of simonkolleite, Zn₅(OH)₈Cl₂·H₂O, which could inhibit the rate determining step, namely charge transfer step, of the electrochemical corrosion process. A model of the evolution process of the product layers formed on zinc was proposed. In addition, the regularity of the corrosion rate of zinc as a function of the NaCl deposition rate can be described by a power function.     

Effects of alternating magnetic field on the corrosion rate and corrosion products of copper

The effects of alternating magnetic field on the corrosion morphologies, corrosion rate, and corrosion products of copper in 3.5% NaCl solution, sea water, and magnetized sea water were investigated using electrochemical test, scanning electron microscopy/energy dispersive analysis system of X-ray (SEM/EDAX), and X-ray diffraction (XRD). The results show that the corrosion rate of copper in magnetized sea water is minimal. Moreover, the surface of the specimen in magnetized sea water is uniform and compact as compared with those in 3.5% NaCl solution and sea water. The corrosion products of copper in magnetized sea water are mainly Cu2O and CuCl2. However, the corrosion products in sea water are CuCl, Cu2Cl(OH)3, and FeCl3·6H2O. The electrochemical corrosion mechanisms of copper in the three media were also discussed.     

Influence of pitting and iron oxide formation during corrosion of carbon steel in unbuffered NaCl solutions

The corrosion evolution over time of a carbon steel rotating disk immersed in aerated NaCl solutions was analyzed using a superposition model. Using this approach, partial polarization curves for iron oxidation and oxygen reduction were synthesized from experimental current-potential data at different corrosion time in order to determine the kinetics parameters, corrosion potential and current density of the underlying anodic and cathodic subprocesses. The distinctive features of the polarization curves are well described in terms of the simplifying assumptions of the model. In particular, the time evolution of the corrosion current density was linked to the morphology of the corroding surface under different NaCl concentrations.     

Studies on waterline corrosion processes and corrosion product characteristics of carbon steel in 3.5 wt% NaCl solution

The waterline corrosion behaviors of carbon steel partially immersed in a 3.5 wt% NaCl solution were investigated using the wire beam electrode technique, and the effects of corrosion products on the processes of waterline corrosion were analyzed. The results demonstrated that the initial stage and development stage of waterline corrosion were mainly controlled by the concentration and diffusion of dissolved oxygen, respectively, and the deceleration stage of waterline corrosion was mainly affected by corrosion products. The main component of the yellow corrosion products was γ-FeOOH, and γ-FeOOH that exhibited a high reduction reactivity could be involved in the cathodic reaction. The black corrosion products were mainly composed of Fe₃O₄ with strong thermodynamic stability and the processes of dissolved oxygen diffusion and ion transports were obviously affected due to the continuous accumulation of Fe₃O₄ on the surface of the electrodes. Polarity reversals were observed on the single electrodes below the waterline, but the reasons for the phenomena were different from each other.     

Corrosion behavior on aluminum alloy LY12 in simulated atmospheric corrosion process

The corrosion behavior of typical high-strength aluminum alloy LY12 was studied by accelerated corrosion tests of cyclic wet-dry-immersion containing media of NaHSO3 and NaCI to simulate the corrosion process in different atmosphere environment, and the corrosion mechanism was also discussed. The main experimental techniques include mass loss, morphological check, analysis of corrosion products and electrochemical measurement. The result shows that the mass loss of LY12, with or without cladding, has linear relationship with test time in the three kinds of chemical media, 0.02 mol/L NaHSO3, 0.006 mol/L NaCl and 0.02 mol/L NaHSO3＋0.006 mol/L NaCl, respectively. A layer of cladding on high-strength aluminum alloy can raise evidently the resistance of atmospheric corrosion. Cl^- can promote pitting generation on the oxide film of LY12 when HOS3 exists, LY12 can react much intensely with HOS3^- derived from anions.     

旋转磁场对海水中铜流动腐蚀的影响(英文)

通过实验室中12d的旋转电磁腐蚀实验,研究海水中铜的流动腐蚀。利用扫描电镜和X射线能量分散分析系统(SEM/EDAX)和X射线衍射仪(XRD)分析铜试样的表面微观结构和相组成,包括空干后腐蚀产物膜中的Cu2O和CuO的组成。结果表明:流动腐蚀过程是坑蚀、扩展、腐蚀产物膜和表面产物溶液,最后是坑蚀。旋转电磁场抑制了铜在海水中的流动腐蚀。     

Moiré based method for real‐time crevice corrosion monitoring

A novel real‐time technique was developed to monitor localized corrosion occurring over a metal surface. It is an optical method based on the Moiré technique that has undergone further improvements and fine tuning for more accurate measurements. Upon testing, good agreements were obtained with the microscopically determined penetration depth. Application for this technique was demonstrated through real‐time monitoring of crevice corrosion activity occurring on the surface of AISI 316 (UNS S31600) stainless steel immersed in 3% NaCl at 60 °C. The crevice was an artificial clear glass/metal crevice with a gap thickness of 5 μm. Based on the findings of these results it was shown that this method can effectively and accurately be used to monitor crevice corrosion.     

Enclosed atmospheric corrosion in ship spaces

Abstract

The process of enclosed atmospheric corrosion within ship spaces is investigated. It is proposed that corrosion rates are influenced mainly by three parameters; time of wetness, salt deposition and temperature. Assuming atmospheric corrosion to be primarily cathodically controlled, it is shown that, as a first approximation, the rate of atmospheric corrosion is linearly proportional to both temperature and salt deposition. This is shown to be consistent with available experimental data. An equation is presented for the prediction of corrosion rates within ship spaces exposed to an enclosed atmosphere, such as cargo holds and ballast tanks, on a per voyage basis. The influencing parameters identified in this study, and the proposed model, provide a starting point for future probabilistic modelling of one component of ship corrosion, namely, enclosed atmospheric corrosion.     

Raman mapping of corrosion products formed onto spring steels during salt spray experiments. A correlation between the scale composition and the corrosion resistance

There is a growing trend in the automotive industry to reduce vehicles weight so as to increase fuel efficiency and therefore reduce CO₂ emissions. For many automotive components such as springs, weight reduction is sought through an increase in the mechanical properties (allowing smaller components size).For ultra high strength springs, a good corrosion resistance becomes essential to avoid surface damage that will be detrimental to the corrosion-fatigue resistance. Corrosion-fatigue failures indeed often initiate on surface defects caused by corrosion in service (corrosion pits). Therefore, while of moderate importance in conventional spring steels, the corrosion resistance of ultra high strength spring steels is of primary importance.Fine changes in steel chemical composition can have an important effect on corrosion resistance. To understand the individual action of each element on the corrosion resistance of spring steels, corrosion products formed on samples exposed to NaCl environments were characterized using Raman spectroscopy, in a purposely designed experimental tool that allows mapping of corrosion products on the steel surface (by nature and mass fraction).Different steel grades were thus characterized after accelerated corrosion tests, and a clear correlation was established between weight loss and the nature of the corrosion products.     

3种有色金属在沈阳地区的大气腐蚀规律

通过Cu，Zn，A1在沈阳地区的大气暴露实验，总结了3种金属的大气腐蚀规律，并讨论了干沉降和湿沉降对金属的大气腐蚀影响。结果表明：Cu，Zn的腐蚀深度与暴露时间呈线性关系；A1的腐蚀深度与暴露时间呈幂指数关系。利用X射线衍射仪和扫描电镜对腐蚀产物的结构和形貌进行分析，并讨论了3种金属大气腐蚀产物的形成过程。