Chloride induced corrosion of reinforcing steel evaluated by concrete resistivity measurements

The chloride threshold (Cl_TH) concentration for rebar corrosion initiation has received extensive attention over the last years. The chloride threshold concentration depends on several factors involving concrete composition and quality, exposure conditions and rebar surface characteristics. As a consequence, many researchers have proposed Cl_TH ranges that take into account the relative influence of each of these many factors. On the other hand, the electrical resistivity of concrete has proven to be an effective parameter that can be used to estimate the risk of reinforcing steel corrosion, particularly when corrosion is induced by chloride attack. The present study is based on a correlation of electrochemical parameters such as corrosion potential (E_corr) and current density (i_corr) together with concrete resistivity (ρ) and chloride concentration data. A relationship between chloride threshold values for rebar corrosion initiation and resistivity values (indicative of concrete quality) is proposed. According to this correlation, when the electrical resistivity of concrete increases from 2 to 100 kΩ cm, the value of Cl_TH increases from 0.44 to 2.32% relative to the weight of cement.     

Bond behaviour of corroded reinforcing steel bars in concrete

The effect of steel corrosion on bond between steel bars and the surrounding concrete was investigated for different corrosion levels. Both pullout tests and finite element analysis were used and the results from the two were compared. An electrolyte corrosion technique was used to accelerate steel corrosion. For confined deformed bars, a medium level (around 4%) of corrosion had no substantial influence on the bond strength, but substantial reduction in bond took place when corrosion increased thereafter to a higher level of around 6%. It is demonstrated that the confinement supplied an effective way to counteract bond loss for corroded steel bars of a medium (around 4% to 6%) corrosion level. The results of finite element analyses, where it was assumed that rust behaved like a granular material, showed a reasonably good agreement with the experiments regarding bond strength and bond stiffness.     

A study on the initiation of pitting corrosion in carbon steel in chloride-containing media using scanning electrochemical probes

Scanning electrochemical probes of corrosion potential and chloride ions were developed for the in situ monitoring of localized corrosion processes of reinforcing steel in NaCl-containing solution. The results indicated that the chloride ions (Cl⁻) preferentially adsorbed and accumulated at the imperfect/defective sites, resulting in initiation and propagation of pitting corrosion on the reinforcing steel surface. An electron microprobe analyzer (EMPA) was used to examine the corrosion morphology and elemental distribution at the corroded location to investigate the origins of the preferential Cl⁻ adsorption and pitting corrosion. By combining the in situ and ex situ images, we concluded that manganese sulfide inclusions in reinforcing steel are the most susceptible defects to pitting corrosion in chloride-containing solution.     

Evaluation of embeddable potential sensor for corrosion monitoring in concrete structures

Embeddable potential sensor based on MnO₂ was assembled and characterised in concrete. The stability, reversibility, polarisability and impedance characteristics have been studied with respect to known reference. The corrosion performance of reinforced steel with respect to MnO₂ sensor was monitored by different electrochemical techniques. Reversibility of MnO₂ sensor indicated that difference of ±5 mV between the forward and reverse scan indicates the better reversibility characteristics in concrete. The rebar potentials (E_R) of steel with respect to MnO₂ are −315 and −525 mV for passive and active conditions of rebar in concrete. The corrosion current from potentiodynamic polarisation and R_ct from a.c. impedance technique clearly differentiated the behaviour of steel embedded in chloride contaminated concrete (active condition) from uncontaminated concrete (passive condition) with respect to MnO₂ sensor. All these studies revealed that corrosion monitoring of steel in concrete using embedded MnO₂ as a better potential sensor for steel in concrete. In addition it is easy to fabricate for amenable miniaturisation, varied configuration as demanded for corrosion monitoring in concrete structures.     

Corrosion measurements of steel reinforcement in concrete exposed to a tropical marine atmosphere

As part of a broad research program, reinforced concrete cylinders of different qualities were exposed to the marine atmosphere of North Peninsula of Yucatán. The cylinders were electrochemically monitored over a period of 56 months. The time for the onset of active corrosion was shorter for rebars in concretes with a high water-to-cement (w/c) ratio compared to that for rebars in low w/c ratio concrete. Results also indicate, as expected, that for equal periods of exposure, nominal corrosion current density (i_corr) values were generally higher for rebar in concrete with higher w/c ratio than those for rebar in low w/c ratio concrete. Analysis of the observed impedance spectra in terms of a modified Randles circuit (in which the ideal capacitor is replaced by a constant phase element (CPE)) appeared to be a reasonable approximation.     

Evaluation on steel bar corrosion embedded in antiwashout underwater concrete containing mineral admixtures

This study aims the evaluation of the corrosion of steel bar embedded in antiwashout underwater concrete, which has rather been neglected to date. To that goal, accelerated steel bar corrosion tests have been performed for three series of steel bar-reinforced antiwashout underwater concrete specimens manufactured with different admixtures and under different environments. The three series of antiwashout underwater concrete were: concrete constituted exclusively by ordinary portland cement (OPC), concrete composed by ordinary portland cement mixed with fly-ash in 20% ratio (FA20) and concrete with ground granulated blast furnace slag is mixed in 50% ratio (BFS50). And, the three different environments were: manufacture in the air, in tap water, and in artificial seawater.Measurement results using half-cell potential surveyor showed that, among all the specimens, steel bar in OPC manufactured in artificial seawater was the first one that exceeded the threshold value proposed by ASTM C 876 with a potential value below − 350 mV after 14 cycles. And, the corresponding corrosion current density and concentration of water soluble chloride were measured as 0.3 μA/cm² and 0.258%. On the other hand, for the other specimens that are FA20 and BFS50, potential values below − 350 mV were observed later at 18 and 20 cycles, respectively.Results confirmed the expectation that mineral admixtures may be more effective in delaying the development of steel bar corrosion in antiwashout underwater concrete.     

Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques

In situ Raman spectroscopy, electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the corrosion behavior of reinforcing steel in simulated concrete pore (SCP) solutions (saturated Ca(OH)₂ solutions). Results indicated that the reinforcing steel remained passive in chloride-free SCP solutions. However, the anodic polarization curve of the steel did not exhibit a stable passive region in the SCP solution with 0.5 M NaCl, the corrosion current density exceeded 0.1 μA cm⁻², the steel surface was unstable with chloride attack and localized corrosion appeared on it with FeCO₃ and Fe₂O₃ as the main corrosion products.     

Effects of cathodic prevention on the chloride threshold for steel corrosion in concrete

This paper presents the results of long-term experimental tests aimed at studying the effects of cathodic prevention on the critical chloride threshold for the onset of pitting corrosion on steel bars in concrete. Cathodic prevention is applied when the structure is new and rebars are still passive being in contact with alkaline and chloride-free concrete. The results obtained showed that even very low values of current densities can increase the critical chloride threshold and, therefore, contribute to increase the service life of reinforced concrete structures in chloride-bearing environments.     

Concentration monitoring and performance of a migratory corrosion inhibitor in steel-reinforced concrete

Inhibitor concentration depth profiles for concrete samples treated with a proprietary migratory corrosion inhibitor (of the Cortec MCI range) are presented. The treated concrete was cored and these cores were then sectioned and crushed before being immersed in distilled water to extract the available inhibitor. The amine concentrations were quantified using an ammonium-sensing electrode and were then related to the inhibitor concentration present. The inhibitor examined, reported to contain a combination of volatile amines and amino carboxylate compounds, was found to readily diffuse through concrete. The inhibitor was subjected to a 5-year trial and found to be effective in suppressing corrosion of steel reinforcement in the presence of high chloride concentrations. The concentration profiles indicate that only relatively low concentrations of inhibitor were required to achieve inhibition in this case.     

Effect of doping by corrosion inhibitors on the morphological properties and the performance against corrosion of polypyrrole electrodeposited on AA6061-T6

This paper describes the electrosynthesis of polypyrrole (PPy) onto AA6061-T6 aluminum alloy from a sulfuric acid solution doped with molybdate anions (MoO₄²⁻) or 8-hydroxyquinoline (8HQ) species. These dopant compounds were chosen as they have been proven to be effective in mitigating the corrosion in chloride medium. The protectiveness of PPy coatings incorporating these corrosion inhibitors within the polymer matrix is discussed. The coatings were morphologically characterized via scanning electron microscopy (SEM) and evaluated electrochemically via polarization in 0.5 M NaCl. The results show that doping PPy with molybdates or 8HQ changes its morphological properties and its effectiveness in preventing passivity loss for AA6061-T6 in chloride media.     

Influence of additives on Cu electrodeposition mechanisms in acid solution: direct current study supported by non-electrochemical measurements

The effect of polyethylene glycol (PEG) and chloride ions on copper electrodeposits is investigated by electrochemical measurements (cyclic voltammetry, current and potential pulses) coupled with an ellipsometric study at open circuit. When PEG is added to the Cu²⁺ solution, the modifications of the copper electrodeposition mechanism can be explained by a polymer-electrode interaction instead of a complex formation in solution. Since ellipsometry has shown no PEG adsorption at least at open circuit, that adsorption is assumed to be potential dependent. Moreover, the efficiency of PEG alone in solution, seems to be decreased when the deposit grows. With Cl⁻ alone, an activation of copper deposition is performed. The simultaneous addition of the two additives induces a blocking effect of the copper reduction that continues on with time. X-ray diffraction, optical microscopy and atomic force microscopy (AFM) carried out complementary results, on bulk deposits obtained from solution with and without these additives. It has been found that a bright, compact and homogeneous coating is only obtained in presence of both additives. In that case, the texture of the deposit is modified and the roughness is significantly decreased to 0.5 μm.     

The influence of mineral admixtures on resistance to corrosion of steel bars in green high-performance concrete

In this paper, the influences of the types, amount and adding approaches of mineral admixtures on pH values, electrical resistance of concrete, anodic polarization potential and mass loss ratio of steel bars in concrete subjected to 50 immersion-drying cycles were investigated. The testing results showed that the addition of mineral admixtures reduced the pH values of the binder pastes in green high-performance concrete (GHPC), especially when two or three types of mineral admixtures were added at the same time (double- or triple-adding approaches), whereas the final pH values were still above the critical breakage pH value of passivation film on the steel bar surface (11.5). Double- and triple-adding approaches also greatly increased the electrical resistance of concrete, which led to a delay in the initial time of corrosion and a decrease in the corrosion rate of steel bars. Additionally, double- and triple-adding mineral admixtures, instead of single-adding, fly ash can reduce the corrosion of steel bars when a large amount of fly-ash replacement was used. All the details of this paper provided a method to reduce or prevent the corrosion of steel bar in concrete, especially for the application in aggressive marine environments.     

Potentiostatic transient technique, a simple approach to estimate the corrosion current density and Stern-Geary constant of reinforcing steel in concrete

The linear polarization resistance (LPR) method, introduced by Stern and Geary, is widely used in determining corrosion rates of steel bars in concrete or synthetic pore solution. The major limitation of this method is that the value of the Tafel slopes, and consequently the Stern-Geary constant (B), is necessary for accurate calculation of the corrosion rate. This paper proposes a simple method for determining the corrosion current density and the Stern-Geary constant, using the results of the potentiostatic transient technique. The effect of the Stern-Geary constant on the corrosion rate of steel bar in concrete is also discussed. Results of this study show that potentiostatic transient method can be used successfully to determine the corrosion rate of steel bars in concrete without using the pre-assumed value of B.     

Corrosion monitoring of reinforcing steel in cement mortar by EIS and ENA

Health degradation by corrosion of steel in civil engineering, especially in rough environment, is a persistent problem. Environment pollution and global warming will exacerbate this problem. The assessment of whole-life costing and residual service life prediction of structures is very important. Pitting corrosion is the most important factor which influences the service life of the reinforced concrete structures in many chloride included environments. Electrochemical impedance spectroscopy (EIS) method is used to study the corrosion process of reinforcing steel in cement mortar. According to the results of the experiments, dispersion and diffusing effect control the electrochemical process of carbon steel corrosion in the cement mortar. By fitting the results with EC, the parameters about CPE and Warburg impedance are calculated. The pitting corrosion behavior of reinforcing steel in cement mortar has been studied by electrochemical noise analysis (ENA) method, the wavelet transform has been employed to analyze the EN data of reinforcing steel in mortar, and the energy distribution plot (EDP) is plotted. The experimental results show that the change of EDP during the corrosion process can qualitatively reveal useful information on corrosion mechanisms.     

Development of a galvanic sensor system for detecting the corrosion damage of the steel embedded in concrete structures: Part 1. Laboratory tests to correlate galvanic current with actual damage

The correlation between sensor output and corrosion rate of reinforcing steel was evaluated by laboratory electrochemical tests in saturated Ca(OH)₂ with 3.5 wt.% NaCl. In this paper, two types of electrochemical probes were developed: galvanic cells containing of steel/copper and steel/stainless steel couples. The corrosion behavior in saturated Ca(OH)₂ solution with and without 3.5 wt.% NaCl addition for the different electrodes was investigated by potentiodynamic test. Weight loss measurement and galvanic corrosion test were conducted to obtain the corrosion rate of reinforcing steel and the charge of sensor in saturated Ca(OH)₂ solution with 3.5 wt.% NaCl addition, respectively.

The results of the potentiodynamic test indicated the possibility of detecting an ingress point of chlorides by measuring the galvanic current. In galvanic corrosion tests, the galvanic current of steel/copper couple was higher than that of steel/stainless steel couple, i.e., the steel/copper sensor is more suitable for high resistance environment. The steel/stainless sensor showed a better linear correlation than the steel/copper sensor. Through the relationship between the sensor system output and the weight loss (mg/cm²) of steel, real corrosion damage of the steel embedded in concrete can be detected.     

Monitoring of steel corrosion in concrete by electrode arrays and electrical resistance probes

In the present work two relatively new methods were implemented, in order to follow exactly the time and spatial evolution of steel corrosion in concrete. Measuring with a coupled electrode array is by some means the advancement of electrochemical noise (EN) with electrically connected micro-electrodes, which are spatially arranged, the assessment of anodic and cathodic currents distribution in time is possible. An electrical resistance (ER) probe can provide general corrosion rate, which is calculated from the thickness reduction; however, its response to localize corrosion is limited. The measurements were performed in concrete specimens, which were exposed to periodic wetting and drying cycles. The results of both used methods were compared and related to the conditions of the micro-electrodes and the ER probes after the test was finished. It was found that micro-electrode arrays can monitor the time and spatial evolution of steel corrosion in concrete. The measured currents reliable indicate the temporal anodic and cathodic activities of individual electrodes, and the assessment of general corrosion rates is also possible. Two characteristic fluctuations of the measured currents from the micro-electrode arrays were defined: slower fluctuations and shorter transients. It is believed that the slower fluctuations were generated by rather general corrosion of the electrodes, whereas the shorter transients were very probably generated by the initiation of pits. In accordance with the results of our previous study, it was confirmed that electrical resistance probes (ER) are able to measure reliably the cumulative corrosion damage, as well as the average general corrosion rate. The general corrosion rates obtained by using ER probes were generally slightly higher than those estimated from the measured currents. It should be mentioned that due to the relatively short duration of the experiments, the reliability of the methods for long-term practical applications still needs to be assessed.     

Study on the corrosion behavior of reinforcing steel in cement mortar by electrochemical noise measurements

The corrosion behavior of reinforcing steel in cement mortar has been studied by electrochemical noise (EN) compared with the electrochemical impedance spectroscopy (EIS). The wavelet transform, as well as the statistical methods including the standard deviation of current noise (σ_I) and noise resistance (R_n), has been employed to analyze the EN data of reinforcing steel in mortar. It is revealed that there exist three different corrosion stages of reinforcing steel in cement mortar, including a competition process between breakdown and repassivation of passive film, a pitting development and an active corrosion during the 20 cyclic immersion and drying tests. The energy distribution plot (EDP) is able to provide useful information about the dominant process for the different corrosion stages.     

Effects of ammonium chloride salt added to mixing water on concrete and reinforced concrete subject to atmospheric corrosion

Studied in this paper is the effect of SO₂ as a pollutant gas on concrete and reinforced concrete specimens at various relative humidity (RH) rates prepared with ideal mixing water (IMW) and IMW+80 mg NH₄⁺ (NH₄Cl) mixing water. The potential values of reinforcing steel were measured throughout 28 days and compressive strength values of concrete specimens in the same medium were determined at the end of the 28th day. SO₂ gas was observed to have a harmful effect at higher RHs on compressive strength of concrete and to make more negative the potential values of reinforcing steel.     

Development of a galvanic sensor system for detecting the corrosion damage of the steel embedded in concrete structure: Part 2. Laboratory electrochemical testing of sensors in concrete

The correlation between sensor output and the corrosion rate of steel bar was confirmed in concrete environment. Open-circuit potential, linear polarization resistance (LPR) measurement and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion behavior of steel bar embedded in concrete. Also, galvanic current measurements of designed sensors were conducted to obtain the charge of sensor embedded in concrete.In this study, the results of corrosion behavior of reinforcing steel showed a consistence among the data obtained by open-circuit potential monitoring, LPR and EIS measurements. Steel/copper sensor showed a good correlation in concrete environment between sensor output and corrosion rate of steel bar. However, there was no relationship between steel/stainless steel sensor output and corrosion rate of steel bar due to the low galvanic current output. Through the relationship between the steel/copper sensor output and the corrosion rate of reinforcing steel, the real corrosion damage of the reinforcing steel can be detected. Consequently, this confirms that the galvanic sensor system is a good method for detection of corrosion in reinforced concrete.