Experimental support for new electro active repair method for reinforced concrete

This paper, describes experiments that form the basis of an invention that aims at improving the durability of conventional (mechanical) repairs to concrete structures suffering from chloride induced corrosion of reinforcing steel. The invention comprises application of a short term, low voltage, DC current before or after concrete is broken out and before repair material is applied. It is an additional step in conventional concrete repair. The application of current will last typically 24 h at a current density of typically 5 A/m² of steel surface area. In laboratory experiments corrosion pits are simulated by placing highly concentrated iron(II)chloride solution in contact with a mortar surface, after which current is applied. The results indicate that this treatment is able to remove 90% or more of the chloride from the simulated pit solutions. Furthermore, the pH has increased from about 3 to more than 12. The combined reduction of chloride content and increase of pH strongly reduces the chloride to hydroxyl ratio of the pore solution and thus the aggressive conditions at the reinforcing steel. After applying alkaline chloride free repair material, this will result in a longer life of the repair, thus reducing the life cycle costs of repaired structures. The process is named EAR, electro active repair.     

Macrocell corrosion of steel in concrete: Characterization of anodic behavior in relation to the chloride content

This study presents the determination of electrochemical properties of active steel in mortar, based on inverse numerical modeling that focuses on their dependency on chloride content. An experimental campaign, consisting of galvanic coupling tests between anode samples contaminated with different chloride concentrations and cathode samples without chlorides, was carried out. Cathode polarization tests allowed for directly determining passive steel electrochemical parameters. Anode polarization tests coupled with a numerical optimization were then performed for quantifying active steel parameters and focusing on chloride's effect on the iron anodic Tafel coefficient. Furthermore, the steel electrochemical properties were successfully used as input parameters to model the galvanic experiments.     

Critical chloride content for reinforced concrete and its relationship to concrete resistivity

The critical chloride content for initiation of reinforcement corrosion is an essential element in service life design and modelling of concrete structures. The critical content is laden with questions regarding its definition, experimental assessment and practical aspects. It should be addressed by a statistical approach. The paper discusses such issues, presents experimental evidence and considers its relationship to the electrical resistivity of concrete. A low concrete resistivity can be theoretically argued to relate to a low critical chloride content. However, only part of the experimental data supports this. The resolution of available data does not allow distinction with regard to the critical content between cement types.     

Polarization resistance measurements of bars embedded in concrete with different chloride concentrations: EIS and DC comparison

The experimental conditions for corrosion rate measurements of reinforcement by means of the polarization resistance technique, R_p, in order to obtain reliable values (in accordance with the gravimetric losses simultaneously measured) must consider some factors as are: the need to subtract ohmic drop generated by the high resistivity of the concrete, the need to wait a certain time after application of the current, the use of a certain sweep rate in order to obtain a quasi‐steady‐state value of the conjugated variable (potential/current), the need to avoid the overlapping with other processes, and the need to use a correct B value in Stern formula. These experimental requirements should be optimized for the individual kinetic of each system. From time to time several papers are published wondering whether R_p measurements in concrete are reliable. Present paper extends the study of the experimental conditions influence in the R_p determination in order to look more in detail to the accuracy of R_p technique. Several sweep rates in potentiodynamic tests, different waiting times with galvanostatic and potentiostatic pulses and different frequencies in electrochemical impedance spectroscopy, EIS, were tested in order to compare the most suitable parameters that provide correct values of the corrosion rate, I_corr.     

Novel corrosion experiments using the wire beam electrode: (III) Measuring electrochemical corrosion parameters from both the metallic and electrolytic phases

The wire beam electrode (WBE) and the scanning reference electrode technique (SRET) have been applied in a novel combination to measure, for the first time, electrochemical parameters simultaneously from both the metallic and electrolytic phases of a corroding metal surface. The objective of this work is to demonstrate the application of this combined WBE-SRET method in obtaining unique information on localised corrosion mechanism, by investigating typical corrosion processes occurring over a mild steel WBE surface exposed to the classic Evans solution. The WBE method was used to map current and potential distributions in the metallic phase, and the SRET was used to map current or potential distribution in the electrolytic phase. It has been found that the combined WBE-SRET method is able to gain useful information on macro-cell electrochemical corrosion processes that involve macro-scale separation of anodes and cathodes. In such macro-cell corrosion systems, maps measured using WBE and SRET were found to correlate with each other and both methods were able to detect the locations of anodic sites. However the movement of the scanning probe during SRET measurements was found to affect the SRET detection of cathodic sites. In micro-cell corrosion systems where the separation of anodic and cathodic sites were less distinct, SRET measurement was found to be insensitive in detecting anodic and cathodic sites, while the WBE method was still able to produce results that correlated well with observed corrosion behaviour. Results obtained from this work suggest that the WBE-SRET method is applicable for understanding the initiation, propagation and electrochemical behaviour of localised corrosion anodes and cathodes, and also their dependence on externally controllable variables, such as solution pH changes and the existence of surface coatings.     

Influence of chloride and moisture content on steel rebar corrosion in concrete

Reinforced mortar samples were exposed in humidity chambers with different relative humidity or exposed in cyclic moisture conditions. The rebars were in an “as received” condition meaning that the preexisting oxide scale were intact. The lowest chloride concentration that initiated corrosion was 1% Cl^? by mass of cement, corrosion was then observed for samples exposed at 97% relative humidity. It is suggested that the corrosion rate decreases when samples are exposed to a relative humidity lower than 97%. The results indicate that threshold levels should be evaluated at rather humid conditions (97%) despite the fact that the maximum corrosion rate at higher chloride levels is observed in the interval 91–94%. For samples exposed to cyclic moisture conditions, a lower chloride concentration was needed to initiate corrosion compared to samples exposed in static moisture conditions.     

Influence of a biopolymer admixture on corrosion behaviour of steel rebars in concrete

Among the multitude of concrete structure pathologies, corrosion of rebars is one of the most important problems of concrete durability. In the context of sustainable development, it appears of primary importance to develop new means to protect the rebars against corrosion. This study aims to develop a new eco‐friendly and corrosion‐inhibiting admixture based on EPS 180 exopolysaccharides, biopolymers used in coatings already studied for the corrosion inhibition on steel in seawater. C15 rebars embedded in CEMI and CEMV cement paste containing EPS 180 were immersed in natural seawater and their electrochemical behaviour was studied using open circuit potential measurements and electrochemical impedance spectroscopy. These tests highlight the decrease of the cathodic reaction kinetics due to the EPS 180 action at the rebars surface, and the absence of effect on the passive layer. Capillary imbibition tests carried out on cement paste and mortars showed that although limiting the imbibition kinetics for cement pastes, the EPS 180 did not influence the water imbibition of mortars. Tests comparing capillary imbibition of soaked cement pastes and mortars with EPS 180 solution and the same samples containing the EPS 180 admixture highlight that the corrosion inhibition induced by EPS 180 admixture is more due to the modification of the cement – rebars interface than to the clogging of the cement porous network.     

Ultrasonic imaging of concrete members using an array system

The use of an ultrasonic array system is described, which can be used combined with 3D reconstruction calculations. In this way ultrasonic reflection and backscatter from the inside of concrete members can be imaged and interpreted. The application of the system is demonstrated for two examples: measuring the concrete cover of utility pipes in a tunnel and the examination of transversal ducts in a bridge plate.     

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.     

Probabilistic considerations on the effect of specimen size on the critical chloride content in reinforced concrete

A probabilistic model was used to predict the critical chloride content (C_crit) for reinforcement corrosion as a function of specimen size. The specimen size is likely to be a reason for the large scatter of C_crit values as well as for the high threshold levels often observed in laboratory setups. Regarding test methods, it is discussed that the common combination of small specimens and low numbers of parallel samples results in poor reproducibility. If experimental data is to be used for service life modelling, the geometrical dimensions of the specimens on which C_crit was measured have to be taken into account.     

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.     

Investigations on the re-passivation of carbon steel in chloride containing concrete in consequence of cathodic polarisation

Although the complex changes at the steel–concrete interface due to cathodic polarisation are widely acknowledged to have a beneficial influence concerning the cathodic protection (CP) of steel in concrete, some questions concerning the repassivation of carbon steel in consequence of cathodic polarisation are still not satisfactorily clarified. In the recent literature, some indications are presented that repassivation occurs after a certain time of polarisation. Therefore, the investigations discussed in this paper aim to clarify, to what extent the re-passivation of carbon steel due to cathodic polarisation occurs, and if the ennoblement of OCP is a sufficient indication for repassivation. In a first step, the corrosion state of five nominal equal test specimens was determined by electrochemical impedance spectroscopy (EIS). After determining the initial corrosion state by evaluating the charge transfer resistance and the polarisation resistance, respectively, the specimens were polarised cathodically. Impedance data were recorded before, during and after polarisation. The impedance data were evaluated by equivalent circuit fitting with special attention to charge transfer resistances and the impact of diffusion on the corrosion and polarisation behaviour. The results indicate that the reduction of oxides and oxygen diffusion during cathodic polarisation has strong impact on the systems behaviour and that repassivation effects occur after switching off the polarisation current and during depolarisation, respectively.     

Detecting critical chloride content in concrete using embedded ion selective electrodes – effect of liquid junction and membrane potentials

When studying critical chloride content in reinforced concrete, the amount of chloride dissolved in the pore solution is an important parameter. Ion selective electrodes offer the possibility of measuring the chloride ion concentration (activity) in the concrete pore solution non‐destructively. However, the potentiometric measurement might be disturbed by, amongst others, diffusion potentials (liquid junction potentials and membrane potentials). Laboratory samples designed to find critical chloride contents often involve chloride ingress by capillary suction, diffusion or migration, and thus chloride and pH profiles are usually present. As a result of these concentration gradients, membrane potentials are established, which markedly affect the determination of the chloride concentration. In addition, liquid junction potentials at the interface of the concrete sample and the reference electrode contribute to the measured potential. Experimental observations in the present work illustrate the effect of liquid junction potentials on the application of ion selective electrodes in concrete. Moreover, the influence of internal membrane potentials has been estimated by a theoretical model.     

Prevention of steel corrosion in concrete exposed to seawater with submerged sacrificial anodes

This paper presents the results of a study of the effectiveness of submerged sacrificial anodes in preventing the onset of pitting corrosion in the emerged part of marine piles. Experimental tests were carried out on reinforced concrete columns with steel embedded both in chloride free concrete and chloride contaminated concrete in order to compare the effects of sacrificial anodes on passive steel and on corroding steel. Results have shown, at least under the present testing conditions, that sacrificial anodes may be more effective in preventing corrosion initiation (i.e. in providing cathodic prevention) than in controlling ongoing pitting corrosion (i.e. in guaranteeing cathodic protection). Monitoring criteria for this type of prevention are also discussed.     

Effects of Tafel slope,exchange current density and electrode potential on the corrosion of steel in concrete

A parametric study is carried out to investigate the effect of variations in anodic and cathodic Tafel slopes, exchange current densities and electrode potentials on the rate of steel corrosion in concrete. The main goal of this investigation is to identify the parameters that have significant influence on steel corrosion rate. Since there is a degree of uncertainty associated with the selection of these parameters, particularly during modelling exercises, it is intended that the results of this study will provide valuable information to engineers and researchers who simulate steel corrosion in concrete. To achieve this goal, the effect of a parameter on the corrosion rate of steel is studied while all other parameters are kept constant at a predefined base case. For each parameter, two extreme cases of anode‐to‐cathode ratio are studied. The investigation revealed that the variations in the anodic electrode potential have the greatest impact on the corrosion rate, followed by the variations in the cathodic Tafel slope.     

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.