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).     

Microstructural properties of the bulk matrix and the steel/cement paste interface in reinforced concrete,maintained in conditions of corrosion and cathodic protection

Although rarely considered, especially within the investigation of steel corrosion phenomena or electrochemical protection techniques in reinforced concrete structures, the concrete bulk matrix has a significant contribution in the global performance of the system “reinforced concrete.” This is especially the case when chloride‐induced corrosion or electrical current flow [as within impressed current cathodic protection (CP)] are involved. In the latter cases, the concrete bulk matrix undergoes significant alterations in chemical composition, electrical properties, and microstructures, thus influencing the overall performance of the system. This work reports on the microstructural investigation of the bulk concrete matrix and the steel/cement paste interface in reinforced concrete, previously subjected to corrosion and CP for 460 days. The emphasis hereby is to evaluate the altered structural properties, i.e., porosity, pore size, permeability of the bulk cement matrix, and the steel/cement paste interface (translated to bond strength) as a result of chloride‐induced corrosion and two types of CP (conventional and pulse), compared to control (non‐corroding, non‐protected) conditions. The research revealed a major contribution and close dependence of all microlevel interfaces on the global performance of reinforced concrete. The electrical current flow (as in CP applications) was found to bring about unfavorable modifications to the material structure, both in the bulk matrix (reducing porosity) and at the steel/cement paste interface (enlarging interfacial gaps). The derived microstructural parameters show that the conventional CP leads to a higher level of structural heterogeneity, whereas the pulse CP exerts minimal or no effects, maintaining the material properties close to the reference (control) conditions, the underlying mechanism being a more homogeneous material microstructure.     

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.     

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.     

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.     

Novel zinc‐rich epoxy paint coatings with hydrated alumina and carbon nanotubes supported polypyrrole for corrosion protection of low carbon steel: Part II: Corrosion prevention behavior of the hybrid paint coatings

Utilization of various types of multi‐walled carbon nanotubes (MWCNTs) in zinc‐rich paints (ZRPs) is presented addressing percolation and porosity related phenomena of traditional ZRPs. Hybrid paint coatings were formulated with 3.21 wt% polypyrrole (PPy) deposited alumina‐MWCNT inhibitor particles (PDAMIPs) and 70 wt% zinc contents. Corrosion protection behavior of the hybrid coatings was investigated by electrochemical impedance spectroscopy (EIS), glow‐discharge optical emission spectroscopy (GD OES), X‐ray photoelectron spectroscopy (XPS), and FT‐Raman spectroscopy. Immersion and salt‐spray chamber tests gave evidence of improved galvanic protection and barrier nature of the hybrid coatings over the conventional ZRPs, whereas inhibited zinc corrosion and ignorable steel corrosion took place besides lower degradation of the binder. Zinc‐rich hybrid paints with either high relative amount of polyelectrolyte‐modified or low proportion of functionalized MWCNTs afforded enhanced corrosion prevention. This result is partly attributed to the nanotube volume fractions around the threshold of infinite cluster formation contributing to electrical percolation and galvanic action of the hybrids. Experimental results are discussed in a broader context on the basis of structure related findings of the PDAMIPs (described in Part I) and in the light of recent literature data. From the newly developed inhibitor particles, some of them are respected as worthy additives for application in hybrid coatings featuring high performance corrosion prevention functionality.