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.     

Corrosion of Carbon Steel and Corrosion-Resistant Rebars in Concrete Structures Under Chloride Ion Attack

Corrosion of reinforced concrete is the most challenging durability problem that threatens reinforced concrete structures, especially structures that are subject to severe environmental conditions (i.e., highway bridges, marine structures, etc.). Corrosion of reinforcing steel leads to cracking and spalling of the concrete cover and billions of dollars are spent every year on repairing such damaged structures. New types of reinforcements have been developed to avoid these high-cost repairs. Thus, it is important to study the corrosion behavior of these new types of reinforcements and compare them to the traditional carbon steel reinforcements. This study aimed at characterizing the corrosion behavior of three competing reinforcing steels; conventional carbon steel, micro-composite steel (MMFX-2) and 316LN stainless steel, through experiments in carbonated and non-carbonated concrete exposed to chloride-laden environments. Synthetic pore water solutions have been used to simulate both cases of sound and carbonated concrete under chloride ions attack. A three-electrode corrosion cell is used for determining the corrosion characteristics and rates. Multiple electrochemical techniques were applied using a Gamry PC4? potentiostat manufactured by Gamry Instruments (Warminster, PA). DC corrosion measurements were applied on samples subjected to fixed chloride concentration in the solution.     

Electrochemical corrosion parameters for active and passive reinforcing steel in carbonated and sound concrete

The electrochemical corrosion parameters, such as corrosion potential, corrosion current density, and the Tafel constants are necessary inputs for the corrosion modeling in reinforced concrete. Literature shows large variability in their values, whereas the data are scarce for the carbonated concrete. This paper presents a range of corrosion parameters for the active steel in carbonated and the passive steel in noncarbonated concrete. Forty-eight singly reinforced concrete cylinders were cast, of which 24 were carbonated and the others were sound samples. Potentiodynamic polarization curves were obtained at three different scan rates and extrapolated to extract the corrosion parameters. To validate these parameters, a macrocell corrosion system was simulated using FEM-based Comsol multiphysics® software. The numerical results were compared to two experimental studies. A natural dispersion in the values of corrosion parameters for both active and passive steels was observed. The average Stern–Geary constant was 54 and 47 mV for active and passive steels, respectively. Numerical simulations with the obtained parameters predicted the macrocell corrosion in partially carbonated concrete with a high accuracy. The presented values of corrosion parameters in this study could help researchers and engineers to simulate the corrosion phenomena in concrete accurately.     

Investigations of an ethanolamine‐based corrosion inhibitor system for surface treatment of reinforced concrete

Laboratory investigations were performed to assess the efficacy of a proprietary ethanolamine‐based corrosion inhibitor system when applied to the surface of reinforced concrete specimens that were chloride‐contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately eighteen months thereafter. Gravimetric measurements of the quantities and distribution of corrosion on the steel were also made on completion of the exposure tests. Analysis of aqueous extracts from treated concrete revealed that the ethanolamine component of the inhibitor system penetrated to depths of more than 15 mm within the concrete. It was found that, for inhibitor‐treated specimens, there was some reduction in the corrosion rate of pre‐corroding steel at low cover depths in non‐carbonated concrete with modest levels of chloride contamination. At higher levels of chloride contamination and in carbonated specimens, however, the ethanolamine‐based inhibitor was apparently ineffective under the conditions investigated.     

Influence of alkali,silicate, and sulfate content of carbonated concrete pore solution on mild steel corrosion behavior

The increase in the rebar corrosion rate due to the concrete carbonation is the major cause of reinforced concrete degradation. The aim of this study was to investigate the corrosion behavior of mild steel rebars in simulated carbonated concrete solution. For this purpose, thermodynamic calculations, electrochemical techniques, gravimetric measurements, and surface analyses were used. Thermodynamic investigations of the nature of the interstitial solution provides an estimation of the influence of sulfate ( ) and alkali (Na⁺, K⁺) content on carbonate alkalinity of the CO₂/H₂O open system (pCO₂ = 0.3 mbar). In this system, calcium‐silicate hydrates (C–S–H) remain thermodynamically unstable and amorphous silica controls silicate aqueous content at 100 ppm. Electrochemical results highlight a decrease in the corrosion rate with increasing carbonate alkalinity and the introduction of silicate. The introduction of sulfate at fixed carbonate alkalinity shows a dual effect: at high carbonate alkalinity, the corrosion rate is increased whereas at low carbonate alkalinity, corrosion rate is decreased. Those results are supported by surface analysis. Authors conclude that silicate and sulfate release from cement hydrates and fixation of alkali on carbonated hydrates are key parameters to estimate mild steel corrosion in carbonated concrete.     

On the effectiveness of realkalisation as a rehabilitation method for corroded reinforced concrete structures

Based on available experience with the use of electrochemical realkalisation (ERA), a fairly recent method for rehabilitating reinforced concrete structures (RCS), carbonated concrete can undoubtedly be realkalised. To the authors' minds, however, the following questions remain unanswered: (a) does ERA always effectively repassivates reinforcements?; (b) can ERA be considered an end or just a means to ensuring RCS durability?; and (c) what is the use of ERA if it cannot stop corrosion? This work was aimed at answering the previous, controversial questions. To this aim, the behaviour in a Ca(OH)₂ saturated solution, and in a sound uncarbonated mortar consisting of 1:3:0.5 cement, sand and water, of reinforcing bars from an RCS that failed through carbonation after 29 years of service life was examined.     

Corrosion inhibitor systems for remedial treatment of reinforced concrete. Part 1: calcium nitrite

Laboratory investigations were performed to assess the efficacy of calcium nitrite as an inhibitor when used in surface treatments applied to reinforced concrete specimens that were chloride contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately 18 months thereafter. On completion of the exposure tests, measurements of corrosion weight losses and their distribution on the steel surfaces were also made. In non-carbonated specimens with high levels of internal chloride and carbonated specimens with even low levels of internal chloride, the surface-applied inhibitor treatment appeared to be ineffective under the conditions of the experiments and enhancement of local corrosion rates was observed in some specimens.     

NO_2~-和Cl~-对模拟混凝土孔隙液中钢筋腐蚀行为的影响

应用极化曲线法和电化学阻抗技术研究了NO_2~-和Cl~-对钢筋在不同pH值的模拟混凝土孔隙液中的腐蚀行为,结果表明,钢筋耐蚀性与溶液的pH值,以及NO_2~-和Cl~-的浓度相关,pH值的降低和Cl~-浓度的增高都会使钢筋的耐蚀性降低。在含Cl~-的模拟液中,随着NO_2~-浓度升高,钢筋腐蚀速率降低,在pH值为12.50和10.50的溶液中,当[NO_2~-]/[Cl~-]≥0.4时,NO_2~-对钢筋具有良好的阻锈作用。     

Steel corrosion in concrete: Determinist modeling of cathodic reaction as a function of water saturation degree

The prediction of the long-term behavior of reinforced concrete structures involved in the nuclear waste storage requires the assessment and the modeling of the corrosion processes of steel reinforcement. This paper deals with the modeling of the cathodic reaction that is one of the main mechanisms of steel rebar corrosion. This model takes into account oxygen reduction and oxygen diffusion through a diffusion barrier (iron oxide and/or carbonated concrete) as a function of water saturation degree. It is demonstrated that corrosion rate of reinforcement embedded in concrete with water saturation degree as low as 0.9 could be under oxygen diffusion control. Thus, transport properties of concrete (aqueous and gaseous phase, dissolved species) are key parameters that must be taken into account to model electrochemical processes on the reinforcement.     

Several questions about electrochemical rehabilitation methods for reinforced concrete structures

Electrochemical realkalisation (ERA) and electrochemical chloride removal (ECR) have shown their capacity to eliminate, in just a few weeks, the causes of corrosion in reinforced concrete structures (RCS), and for this reason are currently receiving very special attention. Nevertheless, the present state of the art has not progressed enough to dissipate doubts about the efficiency of ERA and ECR as electrochemical rehabilitation methods (ERM) for corroding RCS. A series of highly important questions persist, and continue to be cause of controversy among specialists in the construction sector, which can be summed up in one all-encompassing question, namely:

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Is removing the sources of corrosion in RCS sufficient to stop rusting?To obtain a response to this capital question, electrochemical corrosion analysis techniques are used to study the responses of clean and precorroded steel electrodes embedded in small mortar specimens without chloride additions and large mortar slabs with and without chloride contamination. According to the results obtained, ERM are efficient in delaying the start of corrosion if used preventively. However, if applied too late they do not assure the repassivation of rebars with high precorrosion levels and consequently are not useful.

     

Corrosion inhibitor systems for remedial treatment of reinforced concrete. Part 2: sodium monofluorophosphate

Sodium monofluorophosphate (MFP) has been applied in the form of concentrated aqueous solutions to the surfaces of concrete structures with the aim of inhibiting corrosion of embedded reinforcing steel which has become depassivated as a consequence of carbonation and/or chloride contamination. To evaluate the effectiveness of such treatments, a series of laboratory investigations was undertaken with reinforced concrete specimens that were chloride-contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately 18 months thereafter. Gravimetric measurements of the quantities and distribution of corrosion on the steel were also made on completion of the exposure tests. It has been found that there were no marked reductions in the corrosion rates of the steel under the conditions investigated. Analysis of aqueous extracts from the treated concrete specimens by means of ion chromatography revealed that negligible penetration of soluble MFP ions had occurred into any of the specimens. Hydrolysis products of MFP (phosphate and fluoride) were present at significant depths in aqueous extracts of the carbonated concrete specimens but only fluoride was detectable in similarly obtained aqueous extracts of non-carbonated specimens.     

Quantitative characterisation of steel/cement paste interface microstructure and corrosion phenomena in mortars suffering from chloride attack

Chloride ions constitute one of the deleterious agents that may cause or promote corrosion of steel reinforcement in concrete. The influence of chloride ingress on mortar microstructure (including microstructural alterations of hydration products and of pore structure) has been studied by the authors on the basis of cross-section image analysis of reinforced mortar specimens [D.A. Koleva, J. Hu, A.L.A. Fraaij, N. Boshkov, Influences of chloride ions on plain and reinforced mortars, investigated by combined microstructure and electrochemical approaches, Paper 315, Eurocorr 2005, September 4–8 ’05, Lisbon, Portugal]. This paper specifically pursues exploring the morphological aspects and chemical compositions of the corrosion products deposited on steel surface. For this purpose, scanning electron images (SEM) were taken on the cylindrical surface of steel reinforcement and also on the corresponding positions on cement paste surface for visualisation and microstructural investigations of corrosion products. In addition, energy dispersive X-ray analysis (EDXA) and X-ray diffraction (XRD) are employed for quantitative characterisation of the corrosion products at the steel–paste interface. Electrochemical impedance spectroscopy (EIS) is used to estimate the corrosion current and corrosion rate for the reinforced mortars. The EIS measurements are in good agreement with the microstructural observations and quantitative analysis of various corrosion products. The combination of electrochemical measurements with quantitative microstructure analysis of the steel–paste interface constitutes a reliable and useful tool for quantitative characterisation of the interface microstructure and thereby provides better insight into the electrochemical processes during corrosion of the steel reinforcement in concrete.     

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.     

碳化混凝土再碱化过程中钢筋在Ca（OH）2溶液中的电极过程

研究了碳化混凝土再碱化过程中钢筋在Ca(OH)2溶液中的电极表面电化学反应,采用电化学测量技术结合模拟试验考察了电极表面发生各类反应的可能性.结果表明:再碱化过程中,钢筋电极表面的电化学反应与钢筋表面的状态有密切关系,当电极表面存在锈蚀层时,再碱化过程析氢反应和氧化铁的还原同时发生,并使表面氧化层的价态逐渐降低,在电极表面形成金属铁,析氢过程产生的OH-使钢筋周围混凝土的碱性提高.     

Karbonatisierungszellen – Ein Beitrag zur Korrosion von Stahl in karbonatisiertem Beton

Carbonation cells – On the corrosion of steel in carbonated concrete Corrosion of steel in carbonated concrete involves the activity of active-passive galvanic couples (carbonation cells). Carbonation cells consisting of mortar electrodes in wet condition and subjected to wet-dry cycles have been investigated by means of current and potential measurements. The corrosion current can be explained in terms of oxygen diffusion through the mortar cover. The stationary current gives realistic values for the diffusion coefficient of oxygen in concrete. Changes from wet to dry and vice versa always increase the corrosion rate. Electrolytically and gravimetrically determined weight loss are in good agreement only for constant moisture conditions. In case of wetdry cycles oxidation and reduction reactions within the corrosion products are assumed to contribute to the total corrosion loss.     

带锈钢筋再碱化过程中的电极过程研究

研究了带锈钢筋在再碱化过程中的电极表面电化学反应,采用电化学测量技术结合模拟实验考察了电极表面发生的各类反应的可能性;研究了Li+离子对钢筋电极过程的作用,同时考察了带锈钢筋混凝土再碱化后的耐蚀性.结果表明:再碱化过程中,钢筋电极表面的电化学反应与钢筋表面的状态有密切的关系,当电极表面存在锈蚀层时,再碱化过程析氢反应和氧化铁的还原同时发生,并使表面氧化层的价态逐渐降低,并有可能在电极表面形成金属铁.Li+的存在会改善钢筋电极铁与其氧化物之间氧化还原的可逆性,但对带锈钢筋混凝土再碱化后的耐蚀性作用不明显.再碱化对带锈钢筋混凝土的修复具有一定的效果.     

Experimental investigation of time dependent non-linear 3D relationship between critical carbonation depth and corrosion of steel in carbonated concrete

Abstract

This paper aims at the experimental investigation of time dependent non-linear relationship between critical carbonation depth and corrosion rate of steel in carbonated concrete by laboratory controlled experimentation under severe environmental condition. In this research, three-dimensional experimental observations are taken consecutively involving carbonation depth, half-cell potential and elapsed time as well as the gravimetric corrosion mass loss. The experimental observations revealed an interesting non-linear relationship between the above said measurements due to the varying resistivity of carbonated concrete. It is also found that the carbonation induced corrosion does not start until the carbonation depth reaches a certain critical level from the steel rebar and the half-cell potential values become constant after carbonation reaches the critical depth and then start rising again after carbonation reaches the rebar level.     

Stainless steel reinforcing bars – reason for their high pitting corrosion resistance

In harsh chloride bearing environments stainless steel reinforcing bars offer excellent corrosion resistance and very long service life for concrete structures, but the high costs limit a more widespread use. Manganese bearing nickel‐free stainless steels could be a cost‐effective alternative. Whereas the corrosion behavior of stainless steels in alkaline solutions, mortar and concrete is quite well established, only little information on the reasons for the high pitting resistance are available. This work reports the results of pitting potential measurements in solutions simulating alkaline and carbonated concrete on black steel, stainless steel DIN 1.4301, duplex steel DIN 1.4462, and nickel‐free stainless steel DIN 1.4456. Duplex and nickel‐free stainless steels are fully resistant even in 4 M NaCl solutions with pH 13 or higher, the lower grade DIN 1.4301 shows a wide scatter between fully resistant and pitting potentials as low as +0.2 V SCE. In carbonated solutions with pH 9 the nickel‐free DIN 1.4456 shows pitting corrosion at chloride concentrations ≥3 M. This ranking of the pitting resistance can be rationalized based on XPS surface analysis results: both the increase of the Cr(III)oxy‐hydroxide and Mo(VI) contents in the passive film and a marked nickel enrichment beneath the film improve the pitting resistance. The duplex DIN 1.4462 shows the highest pitting resistance, which can be attributed to the very high Cr(III)oxy‐hydroxide, to a medium Mo(VI) content in the film and to a nickel enrichment beneath the film. Upon time, the protective properties of the surface film improve. This beneficial effect of ageing (transformation of the passive film to a less Fe²⁺ containing, more hydrated film) will lead to higher pitting potentials. It can be concluded that short‐term solution experiments give conservative results in terms of resistance to chloride‐induced corrosion in reinforced concrete structures.     

Polarisation behaviour of steel bar samples in concrete in seawater. Part 2: A polarisation model for corrosion evaluation of steel in concrete

In the companion paper [Z.T. Chang, B. Cherry, M. Marosszeky, Polarisation behaviour of steel bar samples in concrete in seawater, Part 1: Experimental measurement of polarisation curves of steel in concrete, Corrosion Science 50(2) (2008) 357-364], influences of the experimental procedure on measured polarisation curves of steel in concrete in seawater were investigated. It was found that an undistorted full polarisation curve of a steel sample in concrete can be obtained by the two-test procedure to conduct separate anodic and cathodic polarisation tests and combine the two partial curves into one curve. However, polarisation curves of steel samples in concrete in seawater were found not to fit with the theoretical curves based on the kinetics of charge transfer reactions. This was considered to be due in the main to the influence of a passive film on the steel surface in concrete. This paper proposes an empirical model for the polarisation behaviour of steel in concrete based on the assumption of two major electrochemical processes taking place at the interfaces of steel/passive-film/concrete: one is the active corrosion process and the other is the passive film growth or dissolution process. Typical curve-fit results are presented using the proposed model to simulate the polarisation behaviour and to evaluate the corrosion rate and Tafel parameters of three types of steel corrosion in seawater: steel bars in concrete, new steel bars and corroded steel bars.     

Utilizing Arghel extract as corrosion inhibitor for reinforced steel in concrete

Inhibition of the corrosion of reinforced steel in concrete in 0.5 M NaCl by Arghel extract has been studied employing different electrochemical techniques in conjunction with optical images photo. Potential‐time measurements showed that introducing of Arghel extract into concrete shifts the potential of reinforced steel to more positive values. Potentiodynamic polarization curves measurements manifested that Arghel extract acts as anodic type inhibitor. Nyquist plots were characterized by a distinct charge transfer and diffusion components. A proposed equivalent circuit was used to analyze the impedance spectra of reinforced steel in concrete in 0.5 M NaCl. Optical images for the cracked lollipops samples of the reinforced steel in concrete that is immersed in 0.5 M NaCl for 18 months showed no corrosion attack even in the presence of a low concentration of Arghel which is in good agreement with the results obtained from the electrochemical techniques.