The beneficial secondary effects of conventional and pulse cathodic protection for reinforced concrete,evidenced by X‐ray and microscopic analysis of the steel surface and the steel/cement paste interface

The present study reports on the investigation of conventional and pulse cathodic protection (CP), in terms of steel surface analysis and investigation of the product layers at the steel/cement paste interface, after a long term (460 days) of conditioning and monitoring. The techniques used were: X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM) and Energy‐dispersive X‐ray (EDX). Wet chemical analysis was used as supportive evidence for ion concentrations in the vicinity of the steel re‐bars. Generally, CP promotes beneficial secondary effects i.e. enhanced OH^? concentration and reduced Cl^? concentration near the steel surface. Cathodic polarization also results in additional deposition of portlandite, which stabilizes the protective properties of the product layer on the steel surface. Consequently, the fundamental mechanisms, underlying the efficiency of CP techniques in reinforced concrete, are strongly related to beneficial secondary effects of CP, affecting the morphology and transformations of these product layers. Since the experimental evidences to support the aforementioned beneficial effects are rather limited, this study investigates the morphology and composition of the “naturally” formed steel surface layers, along with the properties of the steel/cement paste interface, on corroding and protected steel reinforcement (in comparison to reference, non‐corroding, non‐protected conditions) after 460 days of conditioning. For the corroding specimens, the formation and substantial deposition of voluminous corrosion products, with low adherence to the steel surface is relevant (low protective ability), whereas in the protected specimens, a compact and adherent product layer of more stable high valent iron oxides, or calcium substituted such, was observed. To this end, the present work provides the experimental evidence for the fundamental mechanisms, related to the otherwise recognized positive secondary effects of CP in reinforced concrete.     

Conventional and pulse cathodic protection of reinforced concrete: Electrochemical behavior of the steel reinforcement after corrosion and protection

The applicability and efficiency of an alternative for impressed current cathodic protection (CP) for reinforced concrete, based on pulse technology, was investigated. The technique, denoted as pulse CP (pCP), was evaluated on the basis of a comparative analysis to reference (non-corroding), corroding, and conventional CP conditions, in terms of long-term monitoring of electrochemical parameters for the embedded steel with time of corrosion and protection. The hereby reported results are for the total duration of the experiment, i.e., 460 days of conditioning, also presented in comparison with earlier stages. Protection was applied after corrosion was initiated (using corrosion medium of 5% NaCl), at different time intervals (here reported are starting points 60 and 150 days of age). Both CP regimes used current density of 5 or 20 mA/m² steel surface. The pulse CP was applied as a pulse-shaped block current (square wave) with the current itself being the feedback control signal, using 12.5–50% duty cycle at 500 Hz to 1 kHz frequency. Under equal environmental conditions and for a comparatively long period of application, the pulse CP was found to perform as effectively as the conventional CP with regard to electrochemical behavior of the steel reinforcement. Furthermore, the pulse CP technique was found to achieve more rapidly the so called “open circuit potential (OCP) passivity” as a result of an enhanced ion transport (chloride withdrawal) and more favorable cement chemistry (increased alkalinity around the steel reinforcement).     

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.     

In situ 3D monitoring of corrosion on carbon steel and ferritic stainless steel embedded in cement paste

In a X-ray microcomputed tomography study, active corrosion was induced by galvanostatically corroding steel embedded in cement paste. The results give insight into corrosion product build up, crack formation, leaching of products into the cracks and voids, and differences in morphology of corrosion attack in the case of carbon steel or stainless steel reinforcement. Carbon steel was homogeneously etched away with a homogeneous layer of corrosion products forming at the steel/cement paste interface. For ferritic stainless steel, pits were forming, concentrating the corrosion products locally, which led to more extensive damage on the cement paste cover.     

Influence of corrosion on the interface between zinc phosphate steel fiber and cement

The interface bond between steel fibers and concrete matrix is a key factor influencing bearing capacity of steel fiber reinforced concrete (SFRC). In order to improve the interface bond strength and corrosion resistance, a kind of method was put forward by depositing zinc phosphate (ZnPh) coating on steel fiber surface in this paper. The corrosion behavior was investigated in 5% NaCl solution by using linear polarization measurement. Microstructure analysis (SEM and EDX) and fiber pull‐out test in combination with linear polarization measurement were carried out. The results prove that ZnPh coatings fabricated on the carbon steel surface can not only protect steel fiber against corrosion, but also enhance the mechanical interlocking bonds between fibers and matrix.     

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.     

Electrochemical extraction of chlorides from reinforced concrete using a conductive cement paste as the anode

The results of this research show the viability of using a conductive cement paste anode for the electrochemical extraction of chlorides from reinforced concrete with an efficiency similar to that obtained with a classic Ti-RuO₂ anode. The obtained efficiencies are within the typical range of values of overall efficiencies found for such treatments.The thickness of the conductive cement paste anode has a great influence on the capacity of the anode to retain an important part of the extracted chlorides after finishing the electrochemical treatments.     

General corrosion of carbon steel in a synthetic concrete pore solution

In this study, we reviewed our recent work on the general corrosion of carbon steel (P355QL2) overpack material for the isolation of high-level nuclear waste in Belgium's supercontainer concept. By using electrochemical impedance spectroscopy and by optimizing the mixed potential model, which incorporates quantum mechanical tunneling of charge carriers across the barrier layer to describe the kinetics of the partial cathodic process, we evaluated all parameters in the model as a function of independent variables such as voltage, temperature, and pH. By delineating the partial anodic and cathodic processes, we found that the corrosion rate (CR) is independent of voltage over the voltage range from 0.2 to −1.0 V_SHE, which is predicted to be experienced in the repository. Furthermore, the CR is found to increase strongly with decreasing pH and increasing temperature.     

Comparative study on induced macrocell corrosion phenomenon in repaired ordinary reinforced and self-compacting concrete structures

Abstract

This paper aimed at an experimental investigation of the comparative corrosion phenomenon in the reinforcing steel of repaired chloride contaminated self-compacting concrete (SCRC) and ordinary concrete (OC) patches. This research is a continuation of a previous study in which macrocell specimens were prepared with OC having different chloride contaminations simulating the actual patch repair in the construction field. Here, in this research, the same specimens were prepared with SCRC to investigate more deeply the macrocell phenomenon in SCRC, which received limited attention in the past. Four prismatic specimens with two sets of 5 and 3% chloride contaminated SCRC at the two ends were prepared respectively, and the middle portion of these specimens was cast after 24 h with uncontaminated SCRC simulating the actual patch repair in the field. After 1 year of experimental observations of corrosion potentials and corrosion rates, interesting and novel results were obtained in comparison with OC and SCRC specimens.     

Characterisation of the steel concrete interface submitted to chloride‐induced‐corrosion

This paper deals with the characterisation by means of electrochemical, gravimetric and analytical methods of chloride‐induced‐corrosion behaviour of steel coupons embedded in chloride‐containing‐cement pastes. Corrosion rates were estimated from electrochemical measurements as well as gravimetric ones. They vary from 2.6 to 5.7 µm/year for 5 and 10 g/L chloride‐containing‐cement pastes. Analytical characterisations (including optical and electronical microscopy and Raman micro‐spectroscopy) showed that corrosion patterns are not depending on the chloride content of the cement paste (5 and 10 g/L chloride in the interstitial solution). A localised corrosion pattern composed of pits growing inside the metallic substratum, a corrosion products layer (CPL) and a transformed medium (TM) was pointed out. CPL can be divided into two sub‐layers (CPL1 and CPL2), characterised by the presence or absence of calcium coming from the cement matrix.     

Stray current-induced corrosion in cathodic protection installations of steel-reinforced concrete structures: FEM study of the critical parameters

A wide range of parameters was investigated by numerical calculations concerning their impact on DC stray current corrosion of reinforced concrete (RC) structures. A simplified model geometry was used to extract the relevant parameters and their interaction in terms of stray current-affected structures. This study mainly focuses on RC structures that are fitted with cathodic protection installations. The findings reveal a complex interaction between the investigated parameters. The possible relevance of further parameters, which is not the subject of this study, was emphasised.     

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 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.     

Performance of galvanized and stainless steel rebars in concrete under macrocell corrosion conditions

In the recent past, the damage caused by rebar corrosion in concrete structures has been considered as one of the major durability problems affecting the service life of concrete structures. In order to prevent corrosion of steel reinforcement, various types of protective methods have been adopted. One of the protective measures is using galvanized reinforcement in concrete to enhance the service life. In the present study various types of galvanized rebars namely bare – Cold Twisted Deformed (CTD), bare – Thermo Mechanically Treated (TMT), galvanized – Cold Twisted Deformed, Galvanized – Thermo Mechanically Treated, galvanized and chromated – Cold Twisted Deformed, galvanized and chromated – Thermo Mechanically Treated and stainless steel rebars have been evaluated for their corrosion resistance in M30 grade concrete under macro cell corrosion condition over a period of one year. From the studies it has been observed that TMT bars performed better when compared to CTD bars. Among the rebars tested, stainless steel rebar has shown negligible corrosion in chloride contaminated concrete.