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.     

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。     

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。     

Analysis of corrosion resistance behavior of inhibitors in concrete using electrochemical techniques

Reinforced concrete is one of the most durable and cost effective construction materials. However, in high chloride environments, it can suffer from corrosion due to chloride induced breakdown of the normal passive layer protecting the reinforcing steel bars inside concrete. One means of protecting embedded steel reinforcement from chloride induced corrosion is the addition of corrosion inhibiting admixtures. In the present investigation, various inhibitors such as sodium nitrite, zinc oxide, mono ethanol amine, diethanolamine, and triethanol amine have been used in concrete in different percentages. Their effectiveness was then studied using various electrochemical techniques such as rapid chloride ion penetration test, open circuit potential measurement, electrochemical impedance measurement, potentiodynamic polarization measurement, and gravimetric weight loss measurement. The results thus obtained indicate that the addition of inhibitors enhances the corrosion resistance properties.     

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.     

The performance of a 12% chromium steel in concrete in severe marine environments

3CR12, essentially a 12% Cr steel, was used in two series of exposure programmes to assess its performance as reinforcing in concrete. In the first exposure programme, steel and 3CR12 in the pickled and passivated condition were exposed in a specially designed marine climate simulator. Comparative performance after years exposure confirmed 3CR12 as a viable durable reinforcing material for concrete. In the second exposure programme, steel, 3CR12, 316 and 304 stainless steel were exposed in the hot rolled condition (scale intact). Galvanised steel and powder epoxy coated rebar were also exposed. Exposures were carried out at a severely corrosive marine site and in the simulator. Within 2 years, the results from this programme emphasized the need to remove all hot-roll scale from the 3CRI2, the 316 and 304 stainless steel rebars before being used as reinforcing in concrete. Galvanized steel rebars performed poorly. Powder epoxy coated rebars showed severe under-rusting and corrosion. By comparison steel rebars performed extremely badly. Despite the highly alkaline conditions (i.e. the absence of carbonation), chloride penetration caused severe corrosion; the chloride front penetrating through 25 mm of good concrete cover within 2 years.     

Untersuchungen zum kritischen korrosionsauslösenden Chloridgehalt von Stahlfasern in künstlicher Betonporenlösung

Investigations into the critical corrosion‐inducing chloride content of steel fibres in artificial concrete pore solution It is well known, that reinforcement steel in concrete is normally protected against corrosion due to the high pH‐value of the pore solution of the concrete. This alkalinity leads to a passive layer on the steel surface, which prevents further corrosion. The passive layer can be destroyed by chloride ions diffusing into the concrete. The concentration of chloride in the concrete which leads to a destruction of the passive layer and therefore to corrosion of the steel is defined as the critical chloride content. Investigations in artificial concrete pore solutions show that the critical chloride content of black steel is strongly dependent on the pH‐value of the solution: the higher the concentration of the OH⁻‐ions the higher the critical chloride content. For steel fibres earlier investigations have shown, that steel fibres do not corrode in concrete even at high chloride contents. Therefore it could be assumed, that the critical corrosion‐inducing chloride content of steel fibres in concrete is distinctly higher than of conventional reinforcing steel. To verify this assumption the corrosion‐inducing chloride content of steel fibres is investigated in artificial chloride‐containing concrete pore solutions at different pH‐values. 5 different types of steel fibres, 1 lashing wire and as reference 1 reinforcing steel are investigated at 3 different pH‐value ranges. The concentration of chloride within the pore solution is gradually increased in time steps of 12 h. The beginning of corrosion is determined by current as well as potential measurements. Furthermore additional investigations are carried out with intermediate products of the fibre production (steel wires with different diameters) to investigate if the critical chloride content of the wires is increasing gradually with decreasing diameter. The investigations show, that steel fibres in artificial chloride‐containing pore solutions indicate an distinctly increased resistance against chloride‐inducing corrosion compared with conventional reinforcing steel for high pH‐values. With decreasing diameter of wires the critical chloride content increases gradually.     

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.     

Electrochemical chloride removal from reinforced concrete structures and its ability to repassivate prerusted steel surfaces

Gravimetric and electrochemical measurements were used to expose the relationship between the degree of prerusting of reinforcements embedded in chloride‐contaminated mortar or concrete and the efficiency with which they are repassivated once depassivating ions are removed. The results show that, above a certain, ill‐defined rusting threshold, the electrochemical chloride removal does not ensure effective repassivation of reinforcements in the steel/concrete system. Once the passivity of reinforcements embedded in reinforced concrete structures (RCS) is overcome, the typical corrosion rates of the active state seemingly suffice to maintain an acid pH at the metal/rust interface in the bulk of such a strongly alkaline material as concrete. After this local acidification, the metal inside pits probably behaves similarly as it would in an acid solution. As a result, it does not suffice to remove the rusting agent in RCS in order to stop corrosion; rather, the agent must be removed before the first visible signs of deterioration appear.     

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.     

Potentiostatic study of reinforcing steel in chloride contaminated concrete powder solution extracts

This paper presents the findings of an experimental investigation of potentiostatic study on reinforcing steel in chloride contaminated concrete powder solution extracts. Various zones of corrosion for the steel reinforcement at various chloride levels have been identified. In addition the chloride concentration and pH value of these solutions were also measured. The major test variables include steel type, w/c ratio, cement content, and admixed chloride content.     

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.     

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.     

Feasibility of utilizing 2304 duplex stainless steel rebar in seawater concrete: Passivation and corrosion behavior of steel rebar in simulated concrete environments

The feasibility of using 2304 duplex stainless steel rebar in seawater concrete was determined by studying the passivation and corrosion behavior of steel in solutions simulated curing and service stage of concrete, respectively. The results demonstrate that 2304 duplex stainless steel rebar could be used with seawater concrete because of a stable passive film formed on the steel surface during the curing stage of concrete even in the presence of 2 M chloride ions. However, due to the synergistic effect of concrete carbonation, the rebar suffered a corrosive attack by chloride due to the lack of OH^? inhibition.     

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.     

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.     

Effects of tritiated hydrogen peroxide in tritiated water containing Cl and CO3 on behavior of welded type S32550 duplex stainless steel

We report an investigation of the corrosion susceptibility of welded S32550 Duplex stainless steel in the presence of tritiated hydrogen peroxide, chloride and carbonate, which are found in radioactive aqueous solutions. It is well known that a structure transformation occurs during welding, this could lead to localized corrosion of the welded zone. The electrochemical behavior of welded S32550 steel was studied using cyclic voltammetry and electrochemical impedance spectroscopy to provide an indication of mechanisms and oxide layer modifications. Increasing hydrogen peroxide concentration produces several effects. Although the corrosion potential does not change, the prepassive current is higher and, depending on passive potentials and hydrogen peroxide concentration, the passive oxide layer and its characteristics change showing the importance of the radiolytic species in passivity. Also, the breakdown potential shifts towards more positive values on increasing ³H₂O₂ concentration. Thicker passive oxide layers should limit localized corrosion. Examination of the impedance spectra indicates ionic diffusion in the outer oxide passive layer and a diffusion barrier effect for the inner oxide. As the hydrogen peroxide concentration is further increased, these effects appear more pronounced. Carbonate ions should keep the alkaline buffer pH constant giving protection from localized corrosion, and ³H₂O₂ should enhance the characteristics of the inner passive oxide layer. Due to the effects of these two parameters: alkaline pH kept constant at the electrode surface and enhancement of the characteristics of the inner oxide layer by ³H₂O₂, no pitting is observed in presence of chloride ions. Also, an equation, giving the pitting potential limit is derived. The ability of the nucleation sites to propagate as metastable pits is limited by the presence of the ³H₂O₂ and CO²⁻₃ buffers.     

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 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.     

300M和Cr9钢在酸性介质中的电化学性能研究

采用动电位极化、电化学阻抗和金相显微技术研究了300M和一种新型超高强度马氏体钢 (简称Cr9钢)在(H₂SO₄+Na₂SO₄)溶液中的腐蚀规律,以及pH值和Cl^-对其腐蚀行为的影响。研究表明,300M和Cr9钢的腐蚀电位E_corr随pH值增大呈升高趋势,电荷转移电阻R_ct减小,腐蚀电流密度I_corr增大。溶液pH值的降低能加速300M和Cr9钢的腐蚀。在无Cl^-的(H₂SO₄+Na₂SO₄)溶液中,300M发生均匀腐蚀,而Cr9钢则表现为点蚀;Cl^-能促进点蚀的发生,使Cr9钢的阳极反应由钝化转变为活化溶解。Cr9钢中Cr、Mo和Ni元素含量的增加能提高其在酸性介质中的耐蚀性,腐蚀速率明显低于300M钢。