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.     

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.     

Initiation of chloride‐induced corrosion of steel in concrete: role of the interfacial zone

This paper provides a brief review of research aimed at characterising the steel–concrete interfacial zone (SCIZ) and its influence on the susceptibility of the metal to pitting corrosion when concrete is exposed to environments that cause ingress of chloride ions accompanied by leaching of hydroxyl ions. For reinforced concrete made from Portland cements, exposed to aqueous solutions of sodium chloride, the buffering effect of solid calcium hydroxide (portlandite) at pH ～12.6 has been shown to restrain the gradual decline in the hydroxyl ion concentration of the concrete pore solution phase at depths corresponding to the embedded steel. When the concrete is produced under laboratory conditions that are carefully controlled to exclude macroscopic defects from the SCIZ and the steel is cleaned before being embedded, this can lead to observed chloride threshold levels being consistently greater than 1% chloride by mass of cement. The buffering action of cement hydration products formed in the SCIZ is believed to be partly responsible for this high tolerance to chloride‐induced corrosion because it counters the generation of ‘anodic acidity’ that is a necessary condition for stable growth of pits to occur. Translating this behaviour of laboratory specimens to the performance of full‐scale reinforced concrete structures has often proved difficult in the past and there is a need for further research in this area, particularly in relation to the role of non‐traditional cements.     

A study of steel rebars embedded in concrete during 65 years

Several experimental techniques were used to study the corrosion products formed on steel rebars embedded in concrete during 65 years. The research has the objective of understanding the stages of rusting of steel in concrete. Such understanding would provide information concerning the environmental conditions that produce rusting. It was found that rust was composed of two layers: an inner one composed mainly of non-stoichiometric magnetite and probably Ca and Al substituted magnetite firmly adhered to the substrate, and an outer one composed of α- and γ-iron oxyhydroxides, final steel corrosion products. The chemical and mechanical properties of steel rebars and the surrounding concrete were investigated in order to establish the causes of corrosion initiation which were the drop of the concrete pH due to a carbonation process and the loss of steel passivity.     

Corrosion of Reinforcing Bars in Carbonated Concrete

Abstract

In all published studies of cement carbonation there has been general agreement that it must be considered as a cause of generalised corrosion in reinforcements, but quantitative data have been provided in very few cases. In the present work the intensity of attack has been modified by means of the accelerated carbonation of mortar specimens without additives, with 2% CaCl², and with 3% NaNO² It has been shown that a critical level of atmospheric moisture must also be present for considerable attack to occur. The measurement of polarisation resistance (Rp) has been used to evaluate the intensity of corrosion of the reinforcements. This method has already been usefully applied by the authors to investigations of corrosion of steel bars in hardened concrete 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。     

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 injection of organic corrosion inhibitors into concrete

Two organic bases (ethanolamine and guanidine) that are known to act as corrosion inhibitors for steel in aqueous media were introduced into saturated specimens of carbonated and non-carbonated concrete from external electrolytes under the influence of an electrical field applied between embedded steel cathodes and external anodes. The cathodic current density was galvanostatically controlled at values in the range 1-5 A/m² for periods of 3-14 days. Control experiments, in which the corrosion inhibitors were applied to similar saturated concrete surfaces from external electrolyte without current, were also conducted. After treatment, the specimens were sectioned and analysed to determine the concentration profiles of the corrosion inhibitors within the concrete. It was found that the efficiency of injection of both ethanolamine and guanidine under the applied field was far higher in carbonated concrete than in non-carbonated concrete and that, in the carbonated specimens, the inhibitors became concentrated near the embedded steel. In non-carbonated concrete, guanidine penetration was accelerated to a modest extent by the applied field but ethanolamine penetration was not significantly enhanced by the field. These findings were explicable in terms of the influence of the pH values of the pore solutions in the various specimens on the degrees of ionisation of the organic bases concerned and hence on their tendencies to migrate and neutralise cathodically-generated hydroxyl ions.     

水环境混凝土中钢筋腐蚀及其研究的现状与趋势

本文主要对混凝土中钢筋腐蚀的机理及其测量方法的研究现状进行论述。讨论了钢筋腐蚀与混凝土碳化这两种引起混凝土构件破坏的主要因素、基本机理与特征,简要介绍了各种环境因素,尤其是氯离子与碳化对钢筋腐蚀的影响,介绍了几种钢筋腐蚀的电化学原位快速无损检测方法,分析目前钢筋腐蚀研究存在的问题并提出今后发展方向。     

Quantification of Tafel coefficients according to passive/active state of steel carbonation‐induced corrosion in concrete

Statistical quantification of Tafel coefficients is investigated in this study for isolated steel rebar embedded in concrete. The survey is supported by a wide experimental campaign carried out earlier to characterize the passive and active states of carbonation‐induced corrosion of steel. Electrochemical measurements (polarization resistance, corrosion potential, Tafel coefficients) and gravimetric estimations of iron loss were regularly conducted over 417 days on 108 concrete specimens. The statistical analysis reveals that the mean value of Tafel coefficients, both cathodic and anodic, is higher under active corrosion, which seems to contradict the general tendency found for chloride‐induced corrosion, while their coefficient of variation is smaller. The statistical inference was based on the first step of distributions fitting the experimental data and then on the second step of goodness‐of‐fit tests. The most suitable of the distributions proposed were the Burr, Rayleigh, and Gamma distributions. A similar analysis was made for the corrosion potential and polarization resistance. The findings of the study will be valuable for probabilistic approaches to corrosion where probabilistic distributions are required.     

Einflußeiner Verzinkung auf die Korrosion von mit Zementmörtel beschichtetem Stahl in NaCl-Lösung

Effect of galvanizing on the corrosion of steel in concrete immersed in NaCl solution Galvanized or pickled steel sheet specimens were embedded in portland cement mortar of various water cement ratios and curing conditions and then wholly or partially immersed in 0.5 M NaCl solution for 1 to 5 yrs. Free corrosion potentials and electrical resistances have been measured. Immersion conditions and the presence of zinc have a significant effect on the corrosion resistance of the embedded steel sheets. The potentials of the wholly immersed specimens are very negative. Thus, these specimens cannot act as cathodes in corrosion cells, and the steel sheets within the mortar do not corrode. The partially immersed specimens, on the other hand, show very noble potentials. Also in the case of galvanized steel sheets the potentials are shifted to the same positive values in the course of exposure time. Thus, all these specimens can act as cathodes in corrosion cells. Localized corrosion generally occurs at the water/air line. In the case of pickled specimens the mortar is cracked due to growing corrosion products. In the case of galvanized steels the corrosion is retarded significantly. The test results are discussed in detail with respect to practical problems of cell formation, internal and external protection of pipes as well as the corrosion resistance of reinforced concrete.     

Influence of steel-concrete interface condition on galvanic corrosion currents in carbonated concrete

This paper presents specific experiments which were developed in order to assess galvanic currents in macrocell corrosion specimens involving active steel in carbonated concrete and passive steel in sound concrete. The influence of the steel-concrete interface condition on the galvanic current was also experimentally investigated. To focus on macrocell corrosion rate assessment, the initiation time of the corrosion process (concrete carbonation) was accelerated. FEM simulations were carried out in order to enhance the physical comprehension of these corrosion experiments. It was found that, in realistic condition, the electrical coupling of active and passive steel areas leads to high galvanic currents and consequently high corrosion levels according to RILEM recommendation. Moreover, steel-concrete interfacial defaults significantly increase the macrocell driving potential and, therefore, the galvanic corrosion current.     

Environmental influences on linear polarisation corrosion rate measurement in reinforced concrete

The linear polarisation resistance (LPR) method can be used to measure the active rate of corrosion of steel reinforcement in concrete structures. However a single measurement may be sensitive to the ambient environmental conditions and thus may not be representative of the mean annual rate of corrosion. The LPR measurement may be dependent upon the temperature at the time of sampling and on any wetting/drying effects resulting from rainfall and wind or sunshine.Recent studies have examined the behaviour of a series of reinforced concrete specimens subject to chloride contamination or carbonation induced corrosion in a controlled laboratory environment. LPR measurements taken at frequent intervals have been related to a wet/dry cycle imposed upon the specimens to promote corrosion activity. In addition, similar studies have been carried out, of an in situ reinforced concrete specimen exposed to the ambient weather conditions. The study is only partly completed, but interim results show the variability of LPR measurements and the influences the environment may exert on single spot measurements.     

Electrochemical realkalisation for rehabilitation of reinforced concrete structures

In steel reinforced and prestressed concrete structures depassivation of the reinforcing steel can take place due to carbonation of the concrete cover. Depending on humidity and oxygen availability subsequent corrosion reactions will be initiated. Such conditions require measures to exclude corrosion induced damages during the designed lifetime of the structure. In the last few years an electrochemical realkalisation treatment has been proposed as adequate rehabilitation technique for carbonated concrete. This temporary treatment should increase the pH-value of the concrete pore water solution due to penetration of alkaline electrolyte from the concrete surface as well as repassivate the reinforcement due to electro chemical reactions at the steel surface. In order to clarify the different mechanisms taking place during electrochemical realkalisation laboratory tests have been carried out using carbonated reinforced mortar specimens. The investigations were aimed at checking the influence of various parameters, e.g. treatment time and current density, as well as the efficiency and long-term durability of this rehabilitation method.     

Monitoring of corrosion processes in chloride contaminated mortar by electrochemical measurements and X‐ray tomography

Corrosion of steel reinforcement in concrete exposed to chloride containing environments is a serious problem in civil engineering practice. Electrochemical methods, e.g., potential mapping, provide information whether the steel reinforcement is still passive or depassivation has been initiated. By applying such techniques no information on the type of corrosion, its extent and distribution of corrosion products is available. Particular the corrosion progress is a significant problem. Especially in the case of macrocell corrosion in reinforced concrete structures, the development at the anode cannot be separated into corrosion damage resulting from macrocell corrosion or self‐corrosion. Until now also in laboratory tests it is impossible to collect such information without destroying specimens after electrochemical testing was performed. To overcome this problem it was tried to study the steel surface within the mortar specimens by X‐ray tomography (CT). Within the scope of these investigations it could be shown, that X‐ray tomography is suitable to make corrosion pits and their development visible which are embedded in a mortar with a cover thickness of about 35 mm. In this publication the time‐dependent corrosion damage of reinforced steel is documented by X‐ray tomography.     

Epoxy‐coated bars as corrosion control in cracked reinforced concrete

One of the most common corrosion protection methods in reinforcing concrete bars is the application of fusion‐bonded epoxy coatings. Although considerable research has been carried out on the performance of epoxy‐coated bars (ECR), there are still many uncertainties about their performance in cracked concrete. In this experimental program, reinforcing steel bars with six types of epoxy coatings embedded in concrete slabs with a 0.4 mm wide preformed crack intersecting the reinforcing steel at right angles were tested. Results of corrosion potentials, corrosion current density, coating adhesion tests, chloride content, and visual examination after 68 months of exposure to a simulated marine environment are reported. Results revealed that under the studied conditions the ECR did not provide total protection of steel reinforcement in cracked concrete. Their use however, tended to reduce significantly the damage caused by the chloride‐induced corrosion when compared with the uncoated bars embedded in concrete with similar characteristics.     

Chloride threshold for rebar corrosion in concrete with addition of silica fume

The effect of silica fume on the chloride threshold for the initiation of pitting corrosion of steel in concrete was investigated. Laboratory tests were carried out in concrete specimens made with ordinary Portland cement and with 10% of silica fume. Chloride contents up to 2% by mass of cement were added to the mixes, in order to investigate the corrosion rate of embedded bars made of both strengthened and mild steel. A lower chloride threshold was observed in the bars which were embedded in concrete with silica fume compared to those embedded in concrete made of Portland cement.     

Corrosion of reinforcing steel in simulated concrete pore solutions: Effect of carbonation and chloride content

The corrosion susceptibility of as-received reinforcing steel bars (rebars) in solutions simulating the pore liquid of alkaline and carbonated concrete has been studied by means of potentiodynamic polarisation tests and polarisation resistance measurements. The effect of different degrees of carbonation and the presence of several chloride contents in the simulated pore solutions was investigated. Results show the beneficial effect of high alkalinity on the localised corrosion of steel caused by chloride ions. From the results of the potentiodynamic tests a critical chloride concentration above which pitting could take place was evaluated for each solution. The chloride threshold values here found are of the same order than those previously reported in the literature for film-free steel. The results obtained in solutions simulating carbonated concrete showed that under weak carbonation conditions carbon steel does not passivate while in the presence of high levels of carbonate and bicarbonate the resistance to localised corrosion is improved.     

Corrosion behavior of austenitic 304L and 316LN stainless steel clad reinforcing bars in cracked concrete

A study has been conducted on the chloride-induced corrosion behavior of 304L and 316LN stainless steel clad reinforcing bars (rebar) in concrete and in synthetic concrete pore solution. Metallographic examination of the as-received clad bars confirmed a strong metallurgical bond at the core/clad interface and some grain growth interdiffusion of species at the interface. Both bars showed a wide variation in coating thickness around the rebar circumference, from a minimum of 0.32 and 0.60 mm to a maximum of 1.4 and 2.8 mm in the 304L clad and 316LN clad, respectively. The electrochemical results and visual examination after autopsy showed that active corrosion was yet initiated on either the solid and clad stainless steel or carbon steel rebar in the sound noncracked concrete specimens. In contrast, corrosion had initiated in the bars embedded in cracked concrete at the base of the crack and extended along or around the bars. In the concrete and synthetic pore solution tests, the current densities of both solid and clad stainless steel rebar exposed to ∼21% chloride brine solution for days between 400 and 1,500 were similar. This was also the case for current densities of the straight and bent stainless steel bars tested in the synthetic pore solution test.     

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.