Polarisation behaviour of steel bar samples in concrete in seawater. Part 2: A polarisation model for corrosion evaluation of steel in concrete

In the companion paper [Z.T. Chang, B. Cherry, M. Marosszeky, Polarisation behaviour of steel bar samples in concrete in seawater, Part 1: Experimental measurement of polarisation curves of steel in concrete, Corrosion Science 50(2) (2008) 357-364], influences of the experimental procedure on measured polarisation curves of steel in concrete in seawater were investigated. It was found that an undistorted full polarisation curve of a steel sample in concrete can be obtained by the two-test procedure to conduct separate anodic and cathodic polarisation tests and combine the two partial curves into one curve. However, polarisation curves of steel samples in concrete in seawater were found not to fit with the theoretical curves based on the kinetics of charge transfer reactions. This was considered to be due in the main to the influence of a passive film on the steel surface in concrete. This paper proposes an empirical model for the polarisation behaviour of steel in concrete based on the assumption of two major electrochemical processes taking place at the interfaces of steel/passive-film/concrete: one is the active corrosion process and the other is the passive film growth or dissolution process. Typical curve-fit results are presented using the proposed model to simulate the polarisation behaviour and to evaluate the corrosion rate and Tafel parameters of three types of steel corrosion in seawater: steel bars in concrete, new steel bars and corroded steel bars.     

Effect of ecofriendly sealing coat against corrosion protection of steel rebars in concrete

Phosphating is one of the most important chemical conversion treatments for steel, mainly to improve corrosion resistance and paint adhesion and as an absorbing layer for waxes, oils, lacquers, etc. However, phosphate coating are crystalline and porous and need a sealing treatment after phosphating. Chromate sealing is a well known practice, and due to its toxicity, development of an ecofriendly sealing treatment is very essential. This paper focuses on the effect of zinc phosphate chemical conversion coating with the addition of nano-SiO₂ to protect the mild steel rebars against corrosion in chloride contaminated concrete. The coated surfaces were characterised by scanning electron microscopy and X-ray diffraction. Corrosion resistances of coated and uncoated rebars were evaluated by anodic polarisation, linear polarisation resistance, Tafel and alternating current impedance spectroscopy and cyclic polarisation technique. The results indicated that the coated rebars have considerably reduced the corrosion rate even in the presence of 3% chloride environments.     

Electrochemical behavior and the rate of general corrosion of NiAl intermetallic compound in the unbuffered sodium chloride solutions

Highly reproducible Tafel anodic and cathodic plots were obtained on NiAl intermetallic compound in the neutral and nearly neutral unbuffered NaCl solutions. The corrosion potentials and corrosion current densities were determined by the Tafel extrapolation technique at various pH values and concentrations of NaCl. The corrosion current density and Tafel slopes were determined by fitting the equation for the corrosion current density, which involves both anodic and cathodic reactions, to the experimental anodic and cathodic polarization curves in the pre-Tafel region of polarization curves. The results obtained by two methods are in good agreement.     

Transient response analysis of steel in concrete

A new approach is presented for the analysis of galvanostatically induced transients allowing for the rapid evaluation of the corrosion activity of steel in concrete. This method of analysis is based on the iterative fitting of a non-exponential model based on a modified KWW (Kohlrausch-Williams-Watt) formalism. This analysis yields values for the parameters related to corrosion such as the concrete resistance, polarisation resistance, interfacial capacitance and β, the non-ideality exponent.     

Measuring the corrosion rate of steel in concrete – effect of measurement technique,polarisation time and current

Both on‐site investigations and laboratory studies have shown that different corrosion rates are obtained when different commercially available corrosion rate instruments are used. The different electrochemical techniques and the measurement parameters used, i.e. polarisation current and time, are in some studies considered the main reasons for the variations. This paper presents an experimental study on the quantitative effect of polarisation time and current on the measured polarisation resistance – and thus the corrosion current density – of passively and actively corroding steel. Two electrochemical techniques often used in instruments for on‐site corrosion rate measurements are investigated. On passively corroding reinforcement the measured polarisation resistance was for both techniques found to be highly affected by the polarisation time and current and no plateaus at either short or long polarisation times, or low or high polarisation currents were identified. On actively corroding reinforcement a large effect of the polarisation time was also found, but only a minor effect of the polarisation current. The effect of the polarisation time was, however, practically independent of the corrosion rate for actively corroding steel. For both techniques guidelines for polarisation times and currents are given for (on‐site) non‐destructive corrosion rate measurements on reinforcement steel in concrete.     

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.     

Corrosion behavior of low-alloy steel in the presence of Desulfotomaculum sp.

The objective of this study was to determine the effect of sulfate-reducing Desulfotomaculum sp. bacteria isolated from a crude oil field on the corrosion of low-alloy steel. The corrosion rate and mechanism were determined with the use of Tafel slopes, mass loss method and electrochemical impedance spectroscopy (EIS). The formation of the biofilm and the corrosion products on the steel surface was determined with scanning electron microscopy (SEM) micrographs and energy dispersive X-ray spectra (EDS) analysis. It was observed from the Tafel plots that the corrosion potential exhibited a cathodic shift that verifies an increase in the corrosion rates. The semicircles tended to open at lower frequencies in the Nyquist plots which indicates the rupture of the protective film. The corrosion current density reached its maximum value at the 14th hour after the inoculation and decreased afterwards. This was attributed to the accumulation of corrosion products on the surface.     

3D Numerical modelling of steel corrosion in concrete structures

The paper deals with a 3D numerical model for transient analysis of processes after depassivation of reinforcement in concrete, which are relevant for calculation of corrosion rate. The aim of the study is to investigate the influence of the concrete quality, cracking and water saturation in concrete on the current density. The results show that the corrosion rate is higher in poor quality concrete than in good quality concrete. The model predicts that cracks do not influence corrosion rate for the case where the only influence of the crack is on the rate at which oxygen can reach the steel.     

Dithizone and thiosemicarbazide as inhibitors of corrosion of type 304 stainless steel in 1·0M sulphuric acid solution

Abstract

Dithizone and thiosemicarbazide were investigated as inhibitors of the corrosion of type 304 stainless steel in 1·0M sulphuric acid solution by studying weight loss, polarisation curves, and polarisation resistance and using scanning electron microscopy and Auger electron spectroscopy. Various corrosion parameters such as Tafel slopes, corrosion rate, heat of adsorption, and activation energy were evaluated to understand the inhibition mechanism. Inhibition efficiency increased with an increase in concentration of both inhibitors and decreased with an increase in temperature. Both inhibitors seemed to obey the Langmuir adsorption isotherm equation. Dithizone was chemisorbed, whereas thiosemicarbazide was physisorbed on the surface of type 304 stainless steel. Dithizone acted as a mixed inhibitor, while thiosemicarbazide was cathodic in nature.     

Possibilities and problems of in situ techniques for measuring steel corrosion rates in large reinforced concrete structures

In situ measurements of steel corrosion rate in large reinforced concrete structures face difficulties of different types. The paper discusses some of the problems connected with the determination of the true value of the polarisation resistance from (i) the time constant value associated with the corrosion process, and (ii) the use of a guard ring for confining the electrical signal to a definite reinforcement area. In (i), results corroborate the assumption of a time constant value independent of the area affected by the electrical signal, albeit with some exceptions. In (ii), it is shown the great importance of achieving a critical ratio between the current intensities that flow from the guard ring and counter-electrode.     

Electrochemical corrosion parameters for active and passive reinforcing steel in carbonated and sound concrete

The electrochemical corrosion parameters, such as corrosion potential, corrosion current density, and the Tafel constants are necessary inputs for the corrosion modeling in reinforced concrete. Literature shows large variability in their values, whereas the data are scarce for the carbonated concrete. This paper presents a range of corrosion parameters for the active steel in carbonated and the passive steel in noncarbonated concrete. Forty-eight singly reinforced concrete cylinders were cast, of which 24 were carbonated and the others were sound samples. Potentiodynamic polarization curves were obtained at three different scan rates and extrapolated to extract the corrosion parameters. To validate these parameters, a macrocell corrosion system was simulated using FEM-based Comsol multiphysics® software. The numerical results were compared to two experimental studies. A natural dispersion in the values of corrosion parameters for both active and passive steels was observed. The average Stern–Geary constant was 54 and 47 mV for active and passive steels, respectively. Numerical simulations with the obtained parameters predicted the macrocell corrosion in partially carbonated concrete with a high accuracy. The presented values of corrosion parameters in this study could help researchers and engineers to simulate the corrosion phenomena in concrete accurately.     

Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation

The hypothesis that the corrosion of Mg alloys can be adequately estimated using Tafel extrapolation of the polarisation curve is termed herein the electrochemical measurement hypothesis for Mg. In principle, such a hypothesis can be disproved by a single valid counter example. The critical review of Mg corrosion by Song and Atrens in 2003 indicated that, for Mg alloys, Tafel extrapolation had not estimated the corrosion rate reliably. This paper examines the recent literature to further examine the electrochemical measurement hypothesis for Mg. The literature shows that, for Mg alloys, corrosion rates evaluated by Tafel extrapolation from polarisation curves have not agreed with corrosion rates evaluated from weight loss and hydrogen evolution. Typical deviations have been ∼50-90%. These were much larger than the precision of the measurement methods and indicate a need for careful examination of the use of Tafel extrapolation for Mg. For research that nevertheless does intend to use Tafel extrapolation to elucidate corrosion of Mg associated with service, it is strongly recommended that these measurements be complemented by the use of at least two of the three other simple measurement methods: (i) weight loss rate, (ii) hydrogen evolution rate, and (iii) rate of Mg²⁺ leaving the metal surface. There is much better insight for little additional effort.     

Corrosion of reinforcing steel in simulated concrete pore solutions: Effect of carbonation and chloride content

The corrosion susceptibility of as-received reinforcing steel bars (rebars) in solutions simulating the pore liquid of alkaline and carbonated concrete has been studied by means of potentiodynamic polarisation tests and polarisation resistance measurements. The effect of different degrees of carbonation and the presence of several chloride contents in the simulated pore solutions was investigated. Results show the beneficial effect of high alkalinity on the localised corrosion of steel caused by chloride ions. From the results of the potentiodynamic tests a critical chloride concentration above which pitting could take place was evaluated for each solution. The chloride threshold values here found are of the same order than those previously reported in the literature for film-free steel. The results obtained in solutions simulating carbonated concrete showed that under weak carbonation conditions carbon steel does not passivate while in the presence of high levels of carbonate and bicarbonate the resistance to localised corrosion is improved.     

Corrosion monitoring of mild steel in sulphuric acid solutions in presence of some thiazole derivatives – Molecular dynamics, chemical and electrochemical studies

The physical behavior of three selected thiazole derivatives, namely 2-Amino-4-(p-tolyl)thiazole (APT), 2-Methoxy-1,3-thiazole (MTT) and Thiazole-4-carboxaldehyde (TCA) at iron (1 1 0) surface dissolved in aqueous solution were studied via molecular dynamics (MD) simulations. From the calculated binding energies, APT showed preferred adsorption on the steel surface among the three tested thiazole derivatives. The inhibition performance of the three thiazoles on the corrosion of mild steel in 0.5 M H₂SO₄ solutions was investigated at 25 °C. Measurements were conducted under various experimental conditions using weight loss, Tafel polarization and electrochemical impedance spectroscopy. Electrochemical frequency modulation (EFM) technique was also employed here to make accurate determination of the corrosion rates and test validation of the Tafel extrapolation method for measuring corrosion rates. Polarization curves showed that the three thiazole derivatives were of mixed-type inhibitors for mild steel corrosion in 0.5 M H₂SO₄ solution. EFM results were in agreement with other traditional chemical and electrochemical techniques used in corrosion rate measurements. Chemical and electrochemical measurements are consistent with computational study that APT is the most effective inhibitor among the tested thiazoles.     

Investigation of steel corrosion in cracked concrete: Evaluation of macrocell and microcell rates using Tafel polarization response

Inhomogeneous corrosion in reinforced concrete is investigated using a beam with a flexural crack intersecting the reinforcement. An Evans diagram representation of the macrocell corrosion system is developed. The relationship between the current density and the potentials relative to the crack obtained from the Tafel polarization responses of active and passive steel in concrete compares favorably with the experimental values. When both microcell and macrocell mechanisms contribute to metal loss at the crack, the Evans diagram representation indicates that an increase in the macrocell current density results in a decreasing contribution from the local microcell at the macrocell anode.     

The effect of temperature on the corrosion of steel in concrete. Part 2: Model verification and parametric study

A comprehensive model for predicting the corrosion rate of steel in concrete has been developed using the concept of simulated polarization resistance experiments. This model is developed by carrying out a nonlinear regression analysis on data obtained from numerical experiments that are based on the solution of Laplace’s equation in a domain determined by the polarized length of the rebar. This part of the paper provides a comprehensive verification of the developed model and illustrates the application of the model to investigate the coupled effects of parameters affecting corrosion of steel in concrete. The results of the verification study show that the model predictions are in good agreement with the experimental data.     

Quantification of Tafel coefficients according to passive/active state of steel carbonation‐induced corrosion in concrete

Statistical quantification of Tafel coefficients is investigated in this study for isolated steel rebar embedded in concrete. The survey is supported by a wide experimental campaign carried out earlier to characterize the passive and active states of carbonation‐induced corrosion of steel. Electrochemical measurements (polarization resistance, corrosion potential, Tafel coefficients) and gravimetric estimations of iron loss were regularly conducted over 417 days on 108 concrete specimens. The statistical analysis reveals that the mean value of Tafel coefficients, both cathodic and anodic, is higher under active corrosion, which seems to contradict the general tendency found for chloride‐induced corrosion, while their coefficient of variation is smaller. The statistical inference was based on the first step of distributions fitting the experimental data and then on the second step of goodness‐of‐fit tests. The most suitable of the distributions proposed were the Burr, Rayleigh, and Gamma distributions. A similar analysis was made for the corrosion potential and polarization resistance. The findings of the study will be valuable for probabilistic approaches to corrosion where probabilistic distributions are required.     

Potentiostatic study of reinforcing steel in chloride contaminated concrete powder solution extracts

This paper presents the findings of an experimental investigation of potentiostatic study on reinforcing steel in chloride contaminated concrete powder solution extracts. Various zones of corrosion for the steel reinforcement at various chloride levels have been identified. In addition the chloride concentration and pH value of these solutions were also measured. The major test variables include steel type, w/c ratio, cement content, and admixed chloride content.     

Chloride threshold level for corrosion of steel in concrete

The steel rebar inside reinforce concrete structures is susceptible to corrosion when permeation of chloride from deicing salts or seawater results in the chloride content at the surface of the steel exceeding a chloride threshold level (CTL). The CTL is an important influence on the service life of concrete structures exposed to chloride environments. The present study discusses the state of art on the CTL for steel corrosion in concrete, concerning its measurement, representation, influencing factors and methods to enhance the CTL. As the CTL values reported in the majority of previous studies were varied with experimental conditions, corrosion initiation assessment method, the way in which the CTL was represented, direct comparison between the results from different sets and evaluation was subjected to the difficulty. As a result, total chloride by weight of cement or the ratio of [Cl⁻]:[H⁺] is the best presentation of CTL in that these include the aggressiveness of chlorides (i.e. free and bound chlorides) and inhibitive nature of cement matrix. The key factor on CTL was found to be a physical condition of the steel-concrete interface, in terms of entrapped air void content, which is more dominant in CTL rather than chloride binding, buffering capacity of cement matrix or binders. The measures to raise the CTL values using corrosion inhibitor, coating of steel, and electrochemical treatment are also studied.     

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.