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.     

Effect of pulse cathodic protection on corrosion mitigation and electrochemical conditions under a simulated coating disbondment on pipeline steel

Coating disbondments on pipeline steels are regions with high resistivity where conventional cathodic protection (CP) could not fully protect. Therefore, in an attempt to mitigate this challenge, this study investigates the effect of pulse CP on corrosion mitigation and electrochemical conditions under a simulated coating disbondment on X-52 pipeline steel. In this regard, conventional and pulse CP of ?870 mV_SCE were applied to the open mouth of a simulated coating disbondment. For pulse CP, frequencies of 1, 5, and 10 kHz were used. Results showed while the conventional CP was not able to fully protect the 20 cm simulated coating disbondment, for the pulse CP with increase in frequency from 1 to 5 kHz, and from 5 to 10 kHz, improve in CP potential protection under the simulated coating disbondment was achieved. This was accompanied by considerably lower corrosion and a more uniform pH distribution under the simulated coating disbondment.     

Early stage beneficial effects of cathodic protection in concrete structures

Over the last 25 years, cathodic protection (CP) of reinforced concrete structures suffering from chloride induced reinforcement corrosion has shown to be successful and durable. CP current causes steel polarisation, electrochemical reactions and ion transport in the concrete. CP systems are designed based on experience, which results in conservative designs and their performance is a matter of wait‐and‐see. CP systems can be designed for critical aspects and made more economical using numerical models for current and polarisation distribution. Previously, principles of numerical calculations for design of CP systems were reported. The results were satisfactory, except in terms of current density for active corroding systems. This was suggested to be due to neglecting beneficial effects of CP current flow. One of the beneficial effects is pH increase at the steel surface due to oxygen reduction. As the pH increases, the corrosion rate decreases and the current demand decreases. A simple model was set up for this transient process, suggesting that such effects should occur on the time scale of hours to days. This model was validated from start up data of a CP field trial system on part of a bridge. Field results confirmed the modelling proposed here.     

Effects of alternating current interference on cathodic protection potential and its effectiveness for corrosion protection of pipelines

In this work, the effect of alternating current (AC) interference on cathodic protection (CP) potential on a X65 steel in a near-neutral pH bicarbonate solution was investigated, and the CP performance under AC was evaluated by weight-loss measurements. The CP potential applied on the steel cannot be maintained in the presence of AC interference. The shift of the CP potential depends on the applied CP level and AC current density. No matter if the direct current potential of the steel is shifted negatively or positively upon application of AC, the steel suffers from increased corrosion. The AC decreases the effectiveness of CP for corrosion protection. The CP standard at ?0.850?V (copper sulphate electrode) that does not consider the AC interference is not appropriate for AC corrosion protection.     

Numerical design for cathodic protection systems for concrete

Cathodic protection (CP) has become a successful method for the rehabilitation of concrete structures affected by chloride-induced corrosion of reinforcing steel. CP involves applying an electrical current from an external anode through the concrete to the reinforcement. The current causes steel polarisation, electrochemical reactions and ion transport. Normally the anode is placed over relatively large surface areas, including those where the steel is passive. Conventional views assume that protection current will not significantly flow outside the anode area. In many cases this results in a conservative design. This paper presents principles and first results of numerical calculations for design of an example CP system by finite element modelling. The final objective is to develop a tool for more economical CP system design. In particular, a CP system for the protection of local damage in bridges (e.g. at leaking joints) has been simulated. The corroding area with respect to the size of the anode is varied. Current and potential distributions and depolarisation values are predicted, both close to and more distant from the anode. It appears that current densities required to achieve sufficient polarisation are much higher than those usually found in the field. Neglecting time-dependent repassivation processes is likely to be the main cause and further work is needed to include them. The present model can be used with reasonable confidence for preventive application to passive steel.     

Effect of cathodic protection on macrocell currents: A viable method to monitor and control the efficiency of CP?

Corrosion protection of steel reinforcement in concrete structures by cathodic protection (CP) is a cost effective, reliable, and widely accepted method to stop and prevent the corrosion of the steel reinforcement. The efficiency of CP is usually monitored by the “24 h, 100 mV depolarization criterion,” a purely empirical criterion whose implementation is cost and labor intensive and that does not allow online control of CP. Within an extended research project on CP applied to concrete members of a highway bridge exposed to penetrating moisture, three sets of macrocells (MC), each composed of five MC sensors, were installed in conjunction with concrete resistance sensors and silver/silver chloride reference cells. Chloride profiles were determined from the cored or drilled powder originating from the installation of sensors and from drilling cores. Corrosion currents, steel potentials, and concrete resistance were monitored over a period of 1 year before, after installing the CP systems (which remained switched off for half a year for evaluating the effect of the conductive coating), and after start-up of the CP systems. The CP systems applied consist of a moisture resistant conductive coating. As expected CP has a pronounced effect on local MC currents: Anodic MC currents were reduced or changed into cathodic currents, whereas cathodic currents were only weakly influenced. By adjusting the applied protection current all anodic MC currents may be changed into cathodic MC currents. Results indicate that the 100 mV depolarization criterion is a conservative criterion in atmospherically exposed concrete; it is not reliable in strongly wetted concrete. There was no consistent correlation between the CP induced changes in the local MC currents and 24 h depolarization values indicating that large potential shifts induced by CP do not necessarily imply overprotection. Results show that monitoring MC currents before, during, and after CP operation allows to demonstrate in a transparent way the effect of CP on the corrosion of the steel reinforcement. Online monitoring of MC currents is proposed as a viable and comprehensible method to monitor and control the efficiency of CP.     

Effects of SRB on cathodic protection of Q235 steel in soils

The effects of sulfate reducing bacteria (SRB) on cathodic protection (CP) of the Q235 steel in the soils have been studied by bacterial analyses, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and energy‐dispersive X‐ray analysis (EDX). The results showed that the pH value of the soil around the steel gradually increased, the number of SRB and the corrosion rate of the steel decreased, and the CP efficiency increased with the increasing of applied cathodic potential. At the cathodic polarization potential of ?1050 mV, SRB still survived in the soils. At the same potential, the CP efficiency in the soil without SRB was higher than that with SRB, and the corrosion rate of the steel in the soil with SRB was much higher than that without SRB. The cathodic current density applied for the steel in the soil with SRB was bigger than that without SRB at the same cathodic potential.     

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.     

杂散电流干扰和阴极保护作用下碳钢腐蚀规律研究

目的探讨杂散电流和阴极保护二者共同作用对碳钢腐蚀的影响。方法在碳钢管表面手工涂刷涂层并制造小块破损点,研究Q235碳钢在涂层破损后,受单纯直流杂散电流干扰、单纯阴极保护以及二者共同作用时随时间变化的电化学交流阻抗图谱(EIS),通过图谱信息以及图谱数据拟合进行分析。结果所有条件下,Bode图低频阻抗和Nyquist图容抗弧半径都随时间延长而逐渐增加。通过图谱和数据拟合发现,单纯杂散电流条件下,杂散电流越大,电化学阻抗越小,浸泡15天时,20 m A杂散电流条件下的极化电阻达到200 m A条件下的4倍。阴极保护对杂散电流腐蚀具有防护作用,无论是单独施加阴保,还是杂散+阴保共同作用,-1000 m V(vs.CSE)与-850 m V(vs.CSE)横向对比,总是-1000 m V条件下的极化电阻更高。一定程度上,阴保电位越负,极化电阻越大,保护效果越好。结论在一定范围内,不论是单独施加,还是共同作用,总是杂散电流越小,阴极保护电位越负,对碳钢的保护效果越好,腐蚀程度越轻。利用电化学交流阻抗技术监测管道腐蚀状况是可行的。     

Analysis of different factors affecting cathodic protection for deep well casings

This paper introduces a comparative theoretical investigation of the conventional cathodic protection (CP) and the pulse cathodic protection (PCP) systems to show how both of them behave under different operating conditions. The effectiveness of the PCP system is also highlighted for a typical large‐scale configuration as well as some field measurements have been carried out. The performance of PCP system has been analyzed in the light of getting better protection‐current distribution along the protected well casing at reduced anode current together with reducing the stray current (corrosion) at any nearby unprotected structure(s). Many factors have been investigated to show their effects on the performance of the CP system, namely, soil resistivity, voltage pulse waveform and frequency, and multi‐layer soil. In addition, the performance of both the conventional CP and the PCP systems has been compared to that when utilizing unused/abandoned well casing as anode energized by the conventional CP system. The PCP system shows better performance than that of the conventional CP, and a similar performance at high soil resistivity to that when using unused/abandoned well casing. On the other hand, the utilization of the unused/abandoned well casing gives superior performance, especially at low soil resistivities, where the protection‐current profiles of both the conventional CP and the PCP systems decay sharply.     

Nanofabricated multilayer coatings of Zn-Ni alloy for better corrosion protection

As an effort to increase the corrosion resistance of conventional monolayer Zn-Ni alloy coating, the multilayer Zn-Ni alloy coating have been done electrolytically on mild steel (MS), using gelatin and glycerol as additives. Multilayered, or more correctly composition modulated multilayer alloy (CMMA) coatings have been developed using square current pulse. Successive layers of alloys, in nanometric scale having alternately changing composition were fabricated by making the cathode current to cycle between two values, called cyclic cathode current densities (CCCD’s). The coatings having different configuration, in terms of composition and thicknesses of individual layers were developed and their corrosion performances were evaluated by electrochemical methods. The corrosion rate (CR)’s were found to decrease drastically with progressive increase in number of layers (up to 300 layers), and then increased. The coating configurations have been optimized for best protection against corrosion. The CMMA Zn-Ni coating having 300 layers was found to be about 37 times more corrosion resistant than corresponding monolayer alloy, developed from same bath for same time. High protection efficacy of the coatings were attributed to alternate layers of alloys having different surface structure and composition, supported by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) study, respectively. Optimization procedure has been explained, and results are discussed.     

Effect of alternating current on cathodic protection on pipelines

In this work, the effects of alternating current (AC) on the performance of cathodic protection (CP) and the CP potential readings were investigated on a 16Mn pipeline steel in a simulated soil solution. The presence of AC interference decreases the CP effectiveness to protect the steel from corrosion. Only when CP potential is sufficiently negative, the steel is under a complete protection even when the AC current density is 400 A/m². Moreover, the AC would shift CP potential from the designed value. The effect of AC on the CP performance depends on the cathodic potential applied on the steel.     

交流电频率对X80管线钢在酸性土壤模拟溶液中腐蚀行为的影响

通过电化学测试、浸泡实验和表面分析技术研究了交流电频率(50~400 Hz)对X80钢在鹰潭酸性土壤模拟溶液中腐蚀行为的影响。结果表明,随交流电频率的增加,X80钢的腐蚀速率逐渐减小,腐蚀程度减弱。交流电作用下X80钢生成的腐蚀产物疏松、裂纹多,对基体的保护性很差。X80钢的腐蚀电位偏移量随交流电频率的增大而减小。随交流电频率的增大,阴、阳极极化曲线的振荡幅度逐渐减弱。交流电的施加不仅使阴、阳极的电流密度增大,还使阴极反应由混合控制逐渐向活化控制转变。     

Corrosion protection by multilayered conducting polymer coatings

Multilayered coatings, consisting of combinations of the conducting polymers polyaniline (Pani) and polypyrrole (Ppy), were galvanostatically deposited on to both carbon steel and stainless steel. Potentiodynamic polarisation was used to assess the ability of these copolymers to provide an effective barrier to corrosion in chloride environments. For carbon steel the performance of these multilayered coatings on carbon steel were not sufficiently better than for single Pani coatings to justify their more complicated deposition procedures. However, in the case of stainless steels the new multilayered coatings proved to be significantly better than previously reported single Pani coatings, especially at protecting against pitting corrosion. It was found that the degree of protection was a function of the deposition order of the copolymer, with films consisting of a Pani layer over the top of a Ppy layer yielding the best results. Scanning electronic microscopy observations and adhesion measurements, along with the electrochemical data suggested that the ability of a conducting polymer film to act as electronic and chemical barriers were more important in providing corrosion protection than its ability to act as a physical barrier.     

Cathodic protection of buried steel structures: Processes occurring at the steel/soil interface during wet/dry cycles

The behavior of steel coupons buried in soil under cathodic protection (CP) was studied during wet/dry cycles using electrochemical impedance spectroscopy and voltammetry. The coupons were left at open circuit potential for 7 days before applying CP for 51 days at potentials of −0.8 and −1.0 V versus Cu/CuSO₄ on coupons 1 and 2, respectively. Wet/dry cycling was achieved by first saturating the soil with an electrolyte inside a sealed electrochemical cell and by allowing the soil to dry by opening the top lid of the cell for various periods in the experiment. Surface analysis was performed after the experiments by X-ray diffraction and Raman spectroscopy. The soil electrolyte resistance R_s depended mainly on the variations of soil moisture for coupon 1 but was strongly affected by the effects induced by CP for coupon 2. Residual corrosion rates of 17–18 and 7–10 µm/year for coupons 1 and 2, respectively, were estimated via voltammetry. The kinetic parameters vary with the polarization level so that the data obtained with a coupon polarized at a given potential cannot be used to predict the residual corrosion rate of a coupon polarized at another potential.     

Study of criterion for assuring the effectiveness of cathodic protection of buried steel pipelines being interfered with alternative current

Interference of alternative current (AC) on corrosion of X65 steel was investigated in soil. It was observed that the unfavorable effect of interfering AC was able to be effectively inhibited by increasing the direct current density of the cathodic protection (CP) system. A clear correlation was established between the CP current density and the tolerable AC current density. This led to a new criterion for assuring the effectiveness of CP of buried pipelines being interfered with AC. Field experimental results on a buried pipeline running below a 500 kV transmission line showed that the criterion could satisfactorily predict the risk of AC interfering on the CP system.     

Electrochemical corrosion behavior of a novel antibacterial stainless steel

A novel antibacterial stainless steel (ASS) with martenstic microstructure has been recently developed, by controlled copper ion implantation, as a new functional material having broad-spectrum antibacterial properties. The electrochemical corrosion behavior of the ASS in 0.05 mol/L NaCl was assessed using linear polarization and electrochemical impedance spectroscopy (EIS) and compared with that of a conventional stainless steel (SS) without copper ion implantation. The ASS exhibited higher corrosion susceptibility in the chloride medium; with a more negative (active) corrosion potential, higher anodic current density and lower charge transfer and polarization resistance. This has been attributed to the occurrence of copper-catalyzed interfacial reactions. A functional tool, 3-D presentation of EIS data, has been employed in analyzing the electrochemical corrosion processes as well as probing complex interfacial phenomena.     

Comparison of selected inhibitor doped sol–gel coating systems for protection of mild steel

Current legislation around the use of antifouling and anticorrosion coatings has increased the need to find an environment friendly alternative to existing biocide containing pretreatments for steel structures exposed to sea water. Sol–gel technology offers a solution to fouling and corrosion inhibition since sol–gel chemistry lends itself ideally to functionalisation with a variety of components, for example, corrosion inhibitors. In this study, we have utilised the above mentioned approach in order to produce an inhibitor doped sol–gel protective coating on mild steel. The corrosion protection performance of three inhibitors, i.e. SD (Shieldex303), MOLY (Moly-White101ED-PLUS) and ZAPP (Heucophos ZAPP), added individually to a sol–gel, and applied to mild steel Q panels, were evaluated using electrochemical impedance spectroscopy. The inhibitor containing coatings were shown to protect against corrosion of mild steel; the coatings containing the inhibitors Moly and ZAPP were the most effective of the systems tested.

Highlights

? Sol–gel coatings are potential candidate systems for the protection of mild steel substrates.

? Sol–gel chemistry allows a variety of corrosion inhibitors to be incorporated into the sol–gel coating matrix.

? Evaluation of corrosion inhibition efficiency of sol–gel coatings can be assessed using electrochemical impedance spectroscopy (EIS).     

Corrosion study of PVD coatings and conductive polymer deposited on mild steel: Part I: Polypyrrole

Electrochemical deposition of polypyrrole on mild steel substrate was carried out by cyclic voltammetry and galvanostatic technique from neutral aqueous sodium tartrate medium. Homogenous polypyrrole layer for further studies was achieved by galvanostatic technique at constant current density of 5 mA/cm². TiN, CrN and diamond-like carbon (DLC) coatings deposited by physical vapor deposition (PVD) technique on mild steel were used for comparison of corrosion properties with polypyrrole film. Electrochemical synthesis of polypyrrole was also applied as a solution for the PVD coatings porosity problem. Polypyrrole film was successfully deposited on all studied PVD coatings by the galvanostatic technique under special conditions. The protection against corrosion was studied by several methods — measurement of potentiodynamic polarization curves, Tafel plot analysis and electrochemical impedance spectroscopy in 3% NaCl solution.     

Numerical modeling of stray current corrosion of ductile iron pipe induced by foreign cathodic protection system

Stray current corrosion phenomena of ductile iron pipe (DIP) located in the vicinity of cathodically protected steel pipe was assessed using the boundary element method. When all joints in DIP were electrically connected, the maximum corrosion rate was 0.005 mm/y. However, when the joints were isolated, the corrosion rate increased due to the jumping effect of stray current at isolated joints, which resulted in the increase of maximum corrosion rate to 0.87 mm/y at the isolated point. Moreover, the electrical bonding between the DIP and steel pipe could not act effectively but showed an adverse effect of collecting more cathodic protection (CP) currents into the DIP, which eventually jumped out into the soil and resulted in larger amount of stray current corrosion. Therefore it is desirable to apply control methods from the design and construction stage, which include the increase of anodebed and the pipe distance, electrical connection of DIP joints, installation of sacrificial anode at isolated joints, or the application of CP on DIP, etc.