Kritischer korrosionsauslösender Chloridgehalt – Untersuchungen an Mörtelelektroden in chloridhaltigen alkalischen Lösungen

Critical chloride content – Investigations of mortar electrodes in alkaline chloride solutions Although the penetration of chloride ions into the concrete is obstructed by numerous protective mechanisms, the concrete thus a complex multi‐barrier protective system represents, the chloride ions nevertheless succeed it to break through the protecting passive oxide layer of the steel, like the numerous chloride‐induced corrosion damage from building practice clearly document. In a first part results have been outlined concerning the investigations of the reduced corrosion system of steel/concrete pore solution [1]. The present article comprises results of investigations into the critical corrosion‐inducing chloride content that have been obtained by electrochemical investigations of mortar electrodes in alkaline chloride solutions. Finally the findings gained are explained with a view to the relevance they imply for building practice, and particularly for the design of new buildings to be constructed and the assessment of existing structures.     

矿物掺合料对钢筋氯盐腐蚀行为的影响及其作用机理

用水泥提取液模拟混凝土孔隙液,用自腐蚀电位、动电位极化和电化学阻抗技术,研究单掺粉煤灰或矿粉、复掺粉煤灰和矿粉对混凝土中钢筋氯盐腐蚀行为的影响.结果表明,粉煤灰和矿粉均能有效降低钢筋受氯离子腐蚀的风险,减小腐蚀速率,并能不同程度地提高钢筋腐蚀的临界氯离子浓度.抑制氯离子腐蚀能力由强到弱依次为:矿粉>矿粉+粉煤灰>粉煤灰>水泥.且随氯离子浓度的增大,矿粉和粉煤灰的阻锈效率会有不同程度的下降.用矿粉和粉煤灰按适当比例复掺的方法来对抗氯离子腐蚀不仅经济,而且有不错的阻锈效果.     

Detection and identification of concrete cracking during corrosion of reinforced concrete by acoustic emission coupled to the electrochemical techniques

The tenacious oxide passive film, which is formed on the surface of embedded reinforcing steel under high alkaline condition of concrete, protects the steel against corrosion. However, the condition of passivity may be destroyed, due to processes such as leaking out of fluids from concrete, atmospheric carbonation or through the uptake of chloride ions. Passive steel reinforcing corrosion induced by chloride is a well-known problem, especially where chloride-containing admixtures or chloride contaminated aggregate are incorporated into the concrete. The objective of this work is on one hand to study the effect of chloride ions on passivity breakdown of steel, respectively, in simulated concrete pore solution (SCP) and in concrete reinforcement, and on the other hand to reproduce the carbonation phenomena by applying to the concrete samples a heating–cooling cycles. In this context, the acoustic emission coupled to the electrochemical techniques (potentiodynamic and electrochemical impedance spectroscopy (EIS)) are used.

The results show clearly that [Cl⁻]/[OH⁻] ratio of 0.6 is the critical threshold where the depassivation set-up can be initiated. In addition, the carbonation process is very aggressive with chloride ions and shows a perfect correlation with acoustic emission evolution.

A physical model of the reinforcement/electrolyte interface is proposed to describe the behavior of the reinforcement against corrosion in chloride solution.     

Electrochemical rehabilitation methods for reinforced concrete structures: advantages and pitfalls

Abstract

There are still many unresolved issues concerning the efficiency of electrochemical realkalisation and electrochemical chloride removal as electrochemical rehabilitation methods for corroding reinforced concrete structures. The present paper seeks to answer a number of questions which, though seemingly elementary, continue to arouse controversy in scientific, technical and economic communities, despite the vast amount of work that has been devoted to research on corrosion in concrete embedded steel, such as whether corrosion can be stopped once it has started, whether corroded reinforced concrete structures can be repassivated, and whether it is sufficient to remove the sources of corrosion in order to stop rusting. A discussion is conducted on the relationship between the prerusting grade of rebars and the possibility of their repassivation; on whether electrochemical rehabilitation methods treatments are efficient, and if so, when and on whether a simple potential measurement can determine the passive or active state of a rebar. For this purpose an analysis is made, using electrochemical, gravimetric and metallographic techniques, of the response of clean and previously corroded steel electrodes in a Ca(OH)₂ saturated solution with and without a sodium nitrite corrosion inhibitor and in cement mortar. The effectiveness of electrochemical realkalisation and electrochemical chloride removal for repassivating prerusted steel in concrete is found to depend heavily on the prerusting grade.     

Test protocols for migrating corrosion inhibitors (MCI®) in reinforced concrete

Corrosion induced deterioration of steel reinforcement (rebar) in concrete has increasingly become a greater world‐wide concern. This insidious dilemma focuses on the potentially dubious structural integrity of many concrete structures. The steady rise of rebar corrosion and the eventual deterioration can be directly related to several influential factors, some of which include; poor quality construction materials, the increased use of de‐icing salts, severe marine environments and increased atmospheric contaminants, such as carbon dioxide. Over the years various methods have been developed to protect either the rebar or the concrete. Today, the most recent emerging corrosion protection technology is that of Migrating Corrosion Inhibitors (MCIs). Recently, improved test methodologies have been developed which can better assess the effectiveness of corrosion inhibitors. Several of these recent electrochemical and non‐electrochemical test methods were utilized to measure the effects of migrating corrosion inhibitors. This paper includes an explanation of these test methods and presents an overview of the test results.     

Evaluation of the corrosion inhibition of salts of organic acids in alkaline solutions and chloride contaminated concrete

This paper summarizes the results of testing on salts of organic acids for evaluating their use as inhibitors of rebar corrosion in chloride‐contaminated concrete. Initially a screening based on electrochemical tests in alkalinized calcium hydroxide solutions was performed on a number of carboxylic acid salts with different number of carbon atoms in the chain and carboxylic groups, also covering substances with hydroxyl and amine group substituents. The screening was completed by testing on carbon steel rebars in concretes with chlorides and substances added at 1:1 molar ratio, focused on sodium lactate, sodium oxalate and sodium borate for comparison. The monitoring of free corrosion potential and linear polarization resistance of steel bars have confirmed significant inhibition only for lactate. Corrosion was only restricted to occluded zones where the access of substance was limited by disadvantageous geometry, producing shallow attacks. Results of further tests in saturated calcium hydroxide solution are reported in order to assess the inhibition ability of lactate as a function of its content, chloride content and pH.     

Effect of humidity and chloride content on the corrosion of steel embedded in LWA concrete

Measurements have been made with mortar specimens with light aggregates (LWA) and the cements Norcem HS65 and MP30, corresponding to CEM I and CEM II. The w/b ratio was 0.30 and 0.40 and in one mix prewetted LWA was used. The silica fume addition was 8%. The specimens have two sets of electrodes consisting of a 10 mm reinforcing steel and a 10 mm rod of stainless steel. In the start of the experiment the chloride penetration was accelerated by applying a voltage between a negatively charged steel plate within the salt solution and a positively charged net of stainless steel embedded in the concrete above the reinforcing steels. This caused some problems and the set-up was changed to using a Plexiglas brim and a solution of calcium hydroxide and sodium chloride was applied. In the solution, a titanium net was placed and a positive voltage of 12 V was applied between the embedded steels and the net with the titanium net as the positive pole. Measuring galvanic currents, electrochemical potential and polarisation resistances have presented a good picture of the corrosion activity of the embedded steels. There is a distinct effect of the humidity upon the corrosion activity registered by the electrochemical measurements. There is a good relation between the electrochemical measurements and the observed corrosion attacks at the end of the experiments. The LWA concrete with water saturated aggregates showed more corrosion than the corresponding LWA concrete with dry aggregates. The rates of corrosion measured both as a galvanic current and as a function of the polarisation resistance showed that the concrete with watered aggregate concrete had a corrosion rate about twice as high as the corresponding LWA concrete with dry aggregates. There are marked differences in the chloride penetration for the different cements. Effects have been observed on the chloride content of the different concretes. Lower w/b ratio, MP30 cement compared to HS65 and no prewatering of the LWA gave less chloride penetration.     

Electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment

The electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment was investigated by potentiodynamic polarization technique, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results show that uniform corrosion occurs on 300M steel during the electrochemical measurements because no anodic passivation phenomenon is observed on polarization curves within the measurement range. The tests also show that 300M steel is highly susceptible to chloride containing solution, which is characterized by corrosion current density increasing with the addition of chlorides, and corrosion potential shifting towards positive direction and corrosion resistance decreasing, positively suggesting that chloride ions speed up the corrosion rate of 300M steel. Meanwhile corrosion products on the 300M steel surface formed during the salt spray test are too loose and porous to effectively slow down the corrosion rate. Additionally, a schematic structure of uniform corrosion mechanism can explain that 300M steel has better property of stress corrosion cracking (SCC) resistance than stainless steels.     

Study and characterization by acoustic emission and electrochemical measurements of concrete deterioration caused by reinforcement steel corrosion

The durability of reinforced concrete structures becomes a matter of concern, due primarily to the increase of damage by the corrosion of steel reinforcements. This corrosion is not only related to the composition and to the procedure of concrete manufacturing (water/cement, sand/cement, etc.), but also to the aggressive agents as chlorides, carbon dioxide, etc. present in the surrounding medium (Cl⁻, CO₂, etc.). It is well known that the first kind of rebar corrosion (chloride) is more detrimental and that this process contains three basic components: chloride diffusion, electrochemical corrosion and concrete fracture. Therefore the early detection of possible degradation of structures by means of non-destructive testing is essential in order to ensure the functionality of these structures.

This paper presents the results of an experimental investigation on the use of acoustic emission during the corrosion of steel rebars embedded in mortar and immersed in sodium chloride solution. The process of corrosion is accelerated by various imposed potentials and is followed by acoustic emission coupled to electrochemical techniques. The experimental results show that electrochemical techniques can evaluate the corrosive character of the medium used. The acoustic emission showed an activity characteristic of the corrosion initiation phase and the corrosion propagation phase. Thus, it was significantly possible to highlight the acoustic signature of the concrete damage related to the porosity of the mortar and to chloride concentration. The results also show a perfect correlation between the evolution of the acoustic activity and the current of corrosion density.     

Cu-Ni-Sn合金体系油船内底板用耐蚀钢研究

利用扫描电镜（SEM）、电化学、光电子能谱（XPS）、激光原位、透射电镜（TEM）等方法研究了Cu-Ni-Sn体系船体钢在强酸性氯离子环境下的腐蚀行为。结果表明,采用Cu-Ni-Sn的耐蚀合金设计可以显著提高船体钢在强酸性氯离子环境下的耐蚀性,并满足IMO标准的要求;Cu是提高钢耐蚀性的有效元素,其主要机理为其以再沉积颗粒（100～500 nm）的方式在钢的表面富集,降低了钢的溶解速度并抑制点蚀的形核;随着钢中Sn含量的增加,钢的耐蚀性进一步提高,Sn在钢的表面形成了致密的SnO2腐蚀产物保护膜,有效阻止了基体与腐蚀介质的相互作用,进一步抑制了钢的腐蚀。     

Corrosion behavior of steel bar embedded in fly ash concrete

Steel bar embedded in concrete without fly ash and with fly ash was tested under complete immersion, in 3.5 wt.% NaCl solution. Monitoring of open-circuit potential, polarization resistance measurement and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion behavior of steel bar. ASTM C1202 test method was also used to estimate the concrete’s resistance to the penetration of chloride ions. The results obtained from electrochemical tests show that partial replacement of fly ash has led to an enhancement of corrosion resistance and a reduction of corrosion rate due to the decrease of permeability to chloride ions.     

A Synergistic Acceleration of Corrosion of Q235 Carbon Steel Between Magnetization and Extracellular Polymeric Substances

In this work, surface characterization and electrochemical measurement were employed to investigate the effects of magnetic field(MF) on the corrosion of Q235 carbon steel in a NaCl solution containing sulphate-reducing bacteria(SRB) or extracellular polymeric substances(EPS). Results demonstrated that a 150 mT MF enhanced steel corrosion in a SRB-containing NaCl solution by 202% calculated from weight loss with pitting corrosion as the main corrosion type.Either EPS or MF rendered steel corrosion, but a synergistic interaction between MF and EPS boosted up steel corrosion.This synergistic enhancement could be referred to the alteration in orientation of EPS induced by MF. The presence of higher percentage of chloride ions on the carbon steel surface manifested that MF initiated the erosion of chloride ions on the carbon steel coupon.     

A field study of critical chloride content in reinforced concrete with blended binder

This paper presents the results from the investigation of chloride‐induced reinforcement corrosion in concrete slabs after over 13 years exposure in the marine environment. In the beginning of 1990s over 40 reinforced concrete slabs with different types of binder and water/binder ratios were exposed in a marine environment at Swedish west coast. In this study a new rapid technique was used for non‐destructive measurement of corrosion. Based on the results from the non‐destructive measurement, the actual corrosion of steel bars in five concrete slabs was visually examined and the chloride profiles in the penetrating direction as well as at the cover level were measured. The results show that the visible corrosion normally occurred about 10–20 cm under the seawater level, where the oxygen may be sufficiently available for initiating the corrosion. It is also found that chloride may easily penetrate through a poor interface between concrete and mortar spacer and initiate an early corrosion. As a conclusion, although the chloride level 1% by mass of binder may not be the same as the conventionally defined threshold value, it can be taken as the critical level for significant on‐going corrosion that is visible by destructive visual examination, despite types of binder.     

Embedded sensor system to detect chloride permeation in concrete: an overview

Exposure of concrete structures to chloride-bearing solutions such as sea water or de-icing salts brine can affect their durability to stand against deterioration caused by corrosion of steel reinforcement. In order to monitor the chloride ingress into concrete, embedded chloride sensors can be used in concrete structures. Through the sensors, they monitor the initiation of corrosion of steel reinforcement with time, and measure the open circuit potential and polarisation of steel reinforcement, humidity inside the concrete, chloride content and many more. This paper provides an overview of the latest development of chloride permeation measurement in concrete by evaluating the current techniques being used in industry and highlighting a new approach to monitor chloride ion progress in concrete structures wirelessly.     

国产镀锌钢在不同水环境中的腐蚀行为:II反渗透水和调质水

利用开路电位测量、电化学阻抗谱测试技术,结合微观形貌观察,对比研究了国产镀锌钢板在不同反渗透水中的腐蚀行为,镀锌钢在不同进水盐度所得的反渗透水中的腐蚀失效表现出了相似的电化学特征,通过CaCl2、NaCl和NaHCO3等对反渗透水的水质进行调整,改变了镀锌钢的腐蚀失效历程,这可能与腐蚀产物膜的脱落和附着密切相关。     

Chloride threshold level for corrosion of steel in concrete

The steel rebar inside reinforce concrete structures is susceptible to corrosion when permeation of chloride from deicing salts or seawater results in the chloride content at the surface of the steel exceeding a chloride threshold level (CTL). The CTL is an important influence on the service life of concrete structures exposed to chloride environments. The present study discusses the state of art on the CTL for steel corrosion in concrete, concerning its measurement, representation, influencing factors and methods to enhance the CTL. As the CTL values reported in the majority of previous studies were varied with experimental conditions, corrosion initiation assessment method, the way in which the CTL was represented, direct comparison between the results from different sets and evaluation was subjected to the difficulty. As a result, total chloride by weight of cement or the ratio of [Cl⁻]:[H⁺] is the best presentation of CTL in that these include the aggressiveness of chlorides (i.e. free and bound chlorides) and inhibitive nature of cement matrix. The key factor on CTL was found to be a physical condition of the steel-concrete interface, in terms of entrapped air void content, which is more dominant in CTL rather than chloride binding, buffering capacity of cement matrix or binders. The measures to raise the CTL values using corrosion inhibitor, coating of steel, and electrochemical treatment are also studied.     

钢筋阻锈剂的阻锈机理及性能评价的研究进展

钢筋腐蚀是引起钢筋混凝土构筑物提前失效的主要因素,应用钢筋阻锈剂是主要的防腐蚀措施之一。重点介绍了海洋环境中,氯盐的侵蚀机理和阻锈剂的作用机理;讨论了阻锈剂的性能评价方法和应用现状;指出高效且环境友好复合型阻锈剂的合成是今后研究的主要方向,这对于提高我国钢筋混凝土结构耐久性具有重要意义。     

Corrosion resistance of carbon steel in simulated concrete pore solution in presence of 1-dihydroxyethylamino-3-dipropylamino-2-propanol as corrosion inhibitor

The inhibition behaviour of 1-dihydroxyethylamino-3-dipropylamino-2-propanol (HPP) as an environment friendly corrosion inhibitor for reinforcing steel was investigated in simulated concrete pore solution contaminated by 0·1 mol L^?1 Cl^? by means of linear polarisation resistance, electrochemical impedance spectroscopy and cyclic voltammetry (CV). The surface morphology and corrosion products were also examined by scanning electron microscopy and X-ray diffraction (XRD). The results show that HPP can effectively inhibit the corrosion of reinforcing steel. The CV interpreted the corrosion inhibitor by restraining the reaction of cathodic reduction and anodic oxide. The XRD shows that the corrosion inhibitor reduces Cl^? adsorption on oxide film and reduces the production of corrosion products. In the conditions of this investigation, HPP behaves as an anodic corrosion inhibitor, protecting steel against corrosion in chloride contaminated environments.     

Corrosion inhibition behaviour of thiourea derivatives in acid media against mild steel deterioration: An overview

This paper summarizes the inhibitor activity of various reported thiourea derivatives in acid media used against the deterioration of mild steel. Acid solutions have been extensively employed in manufacturing and many industrial processes for pickling and removal of undesirable scale. Mild steel is highly susceptible to corrosion in such aggressive acid media. The additives such as inhibitors are widely employed in those cases to reduce the extent of corrosion as much as possible. The survey of literature on organic inhibitors clearly indicates the potential usage of thiourea derivatives as inhibitors of mild steel corrosion. The influence of physical-chemical properties on the inhibition activity of thiourea derivatives has been discussed. This information is highly useful for different industrial applications where good performing inhibitors are being required for protecting mild steel from aggressive acid media.     

钢筋混凝土构筑物电化学保护的新进展

综述了钢筋混凝土构筑物电化学保护的发展和现状,包括牺牲阳极系统和外加电流系统。内容涉及对不同类型、不同龄期构筑物的保护标准、保护参数选择、保护效果的评价以及检测、监测等诸方面。认为有必要加强电化学驱氯、电化学再碱化等新技术的研究;根据构筑物的不同使用环境,采用多种有效的、综合的保护措施。