Environmental factors affecting the corrosion behavior of reinforcing steel III. Measurement of pitting corrosion currents of steel in Ca(OH)2 solutions under natural corrosion conditions

Using a simple electrolytic cell, the pitting corrosion current of reinforcing steel is measured in Ca(OH)₂ solutions in presence of chloride and sulfate as aggressive ions. Pitting corrosion current starts to flow after an induction period which depends on the concentration of both the aggressive and the passivating anions. The pitting corrosion current densities reach steady-state values which depend also on the type and concentration of the corrosive and passivating anions. The corrosive action of the aggressive species decreased in the order: SO₄²⁻ > Cl⁻. Corrosion of the steel is found to be governed by a single electron transfer reaction. Raising the temperature decreases the induction period associated with pit initiation and increases the corrosion current associated with pit propagation. From Arrhenius plots, the activation energies for both pit initiation and pit propagation in presence of chloride and sulfate ions are calculated.     

Corrosion behaviour in alkaline medium of zinc phosphate coated steel obtained by cathodic electrochemical treatment

The present work evaluated the ability of zinc phosphate coating, obtained by cathodic electrochemical treatment, to protect mild steel rebar against the localized attack generated by chloride ions in alkaline medium. The corrosion behaviour of coated steel was assessed by open circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy. The chemical composition and the morphology of the coated surfaces were evaluated by X-ray diffraction and scanning electron microscopy. Cathodically phosphated mild steel rebar have been studied in alkaline solution with and without chloride simulating the concrete pore solution. For these conditions, the results showed that the slow dissolution of the coating generates the formation of calcium hydroxyzincate (Ca(Zn(OH)₃)₂·2H₂O). After a long immersion time in alkaline solution with and without Cl⁻, the coating is dense and provides an effective corrosion resistance compared to mild steel rebar.     

The inhibition activity of ascorbic acid towards corrosion of steel in alkaline media containing chloride ions

The activity of ascorbic acid towards steel corrosion in saturated Ca(OH)₂ solution containing chloride ions was investigated in this study. Concentration and time dependence of the protective properties of the passive film were acquired by electrochemical impedance spectroscopy. The best inhibitive performance, i.e. the longest pitting initiation time was obtained in the presence of 10⁻³ M ascorbic acid, while both lower and higher concentrations showed shortening of the pitting-free period. The overall behaviour of ascorbic acid was attributed to its ability to form chelates of various solubility having various metal/ligand ratios and oxidation states of the chelated iron. The assumption of ascorbic acid assisted reductive dissolution of the passive layer at higher inhibitor concentrations was confirmed by cyclic voltammetry and ATR FTIR spectroscopy. It is proposed that the overall inhibitive effect at lower concentrations is due to the formation of insoluble surface chelates and the effective blocking of the Cl⁻ adsorption at the surface of passive film. A pronounced inhibitive effect observed after the pitting had initiated was ascribed to the formation of a resistive film at the pitted area.     

Improved corrosion resistance in simulated concrete pore solution of surface nanocrystallized rebar fabricated by wire-brushing

Continuous surface nanocrystallization (SNC) of rebar was achieved through wire-brushing process. A uniform NC layer with thickness of 25 μm and average grain size of 50 nm was formed on the rebar surface. Due to the enhanced passivation performance of the NC layer, corrosion resistance of the SNC rebar was significantly improved in Cl⁻-containing saturated Ca(OH)₂ solution. High-energetic crystal defects of the nano-grains leads to the faster passivation and enhanced stability of the passive film of the SNC rebar.     

An electrochemical and ellipsometric investigation of surface films grown on iron in saturated calcium hydroxide solutions with or without chloride ions

Ellipsometric studies combined with electrochemical measurements of films grown on Armco iron in de-aerated saturated Ca(OH)₂ solution were performed. It was found that the surface film formed on iron in contact with aqueous saturated solution of calcium hydroxide at anodic potentials exhibits a complex index of refraction of 1.7 (1-0.07i), which is not affected by small additions of chloride ions to the electrolyte. However, at CaCl₂ concentrations larger than 0.05 M, the refractive index is reduced to n = 1.6. Presumably, under these conditions a layer of iron oxyhydroxide with incorporated Ca(OH)₂ forms on the surface of iron. The outer gelatinous layer of corrosion products formed on the top of the oxyhydroxide layer exhibits a still lower index of refraction n = 1.34. At open circuit potential, in Cl^?-free solution, the film exhibits n = 1.43, suggesting that it is composed of iron hydroxide. This layer is absent in solution containing Cl^?. In this case, the refractive index of the film is about 1.34.     

Electrochemical studies of steel in cement mortar containing chloride and micro-silica

Steel electrodes have been exposed for 3.5 years in cement mortar with and without chloride and ELKEM micro-silica. Corrosion potentials in mortar without Cl⁻ varied between −0.1 and +0.06 V(SCE), indicating passivity. One percentage of cement weight of Cl⁻ reduced the corrosion potentials to about −0.2 V(SCE). Micro-silica in chloride containing mortar increased the severity of corrosion the first year. However, after 2 years exposure reduction of interconnected porosity and increased resistivity caused by 15% micro-silica, raised the corrosion potentials and counteracted chloride-attack.The polarisation resistance was undefined, the apparent values varying with the technique and parameters used.     

Pore solution of concrete: The equilibrium of bound and free chloride

The chloride threshold values of concrete specified in the regulations are based on the total chloride content of the concrete. As only the chloride dissolved in the pore solution can initiate corrosion, the investigations focused on the chloride concentration of the pore solution. It was further investigated if the answer to the question — why chloride is taken up by concrete exposed to de‐icing salts relatively quickly but is only slowly ‘washed out’ during summer — can be found in the chloride/cement‐binding interactions. The results showed that the residual chloride concentration depends in particular on the OH^? concentration of the pore solution. The results further showed that the same binding mechanisms exist regardless of whether the chloride is mixed to the cement or added subsequently via diffusion. Other results suggested that one of the causes why chloride is taken up faster than it is washed out from concrete by rainwater are the binding interactions as well. As regards the assessment of the corrosion risk, the results showed that both the Cl^? concentration and the Cl^?/OH^? ratio of the pore solution varied between samples made of the same cement and containing the same total chloride content. These results illustrate very well that a certain total chloride content alone is not a suitable criterion for the assessment of corrosion risk and that other factors of influence must be taken into account as well.     

Corrosion resistance of carbon steel in simulated concrete pore solution in presence of 1-dihydroxyethylamino-3-dipropylamino-2-propanol as corrosion inhibitor

The inhibition behaviour of 1-dihydroxyethylamino-3-dipropylamino-2-propanol (HPP) as an environment friendly corrosion inhibitor for reinforcing steel was investigated in simulated concrete pore solution contaminated by 0·1 mol L^?1 Cl^? by means of linear polarisation resistance, electrochemical impedance spectroscopy and cyclic voltammetry (CV). The surface morphology and corrosion products were also examined by scanning electron microscopy and X-ray diffraction (XRD). The results show that HPP can effectively inhibit the corrosion of reinforcing steel. The CV interpreted the corrosion inhibitor by restraining the reaction of cathodic reduction and anodic oxide. The XRD shows that the corrosion inhibitor reduces Cl^? adsorption on oxide film and reduces the production of corrosion products. In the conditions of this investigation, HPP behaves as an anodic corrosion inhibitor, protecting steel against corrosion in chloride contaminated environments.     

Environmental factors affecting the corrosion behavior of reinforcing steel. IV. Variation in the pitting corrosion current in relation to the concentration of the aggressive and the inhibitive anions

The pitting corrosion current of reinforcing steel is measured under natural corrosion conditions in Ca(OH)₂ solutions in presence of Cl⁻ as aggressive ions and as inhibiting anions. The corrosion current starts to flow after an induction period which depends on solution composition (concentration, pH and presence or absence of the aggressive and the inhibiting anions). The limiting corrosion currents increase with increasing the Cl⁻ ion concentration and decrease with increasing the pH and inhibiting ions concentration. The inhibition efficiency of the studied inhibiting ions increases in the following order: , and depends on the way by which the inhibitor is added to the solution. Injection of the inhibiting anions in solution causes repassivation of the pre-formed pits through competition with Cl⁻ ions for adsorption sites on metal oxide surface. The adsorbability constant and the free energy of repassivation of the inhibiting anions are calculated.     

Corrosion of anodically polarized Zn-Al alloys in saturated Ca(OH)2 containing Cl-

Cast Zn-Al alloys containing 0%, 20%, 40%, 55%, 80% and 100% aluminium have been anodically polarized in saturated Ca(OH)₂ containing Cl^- and the conditions for corrosion and for pitting with respect to alloy composition, chloride concentration and alloy microstructure broadly defined. Pure zinc has a large passivation range which shows an etch-pitting-passivation process above about 0.02 M Cl^-. Pure aluminium has a poorly defined passive region with a large passive current and the presence of Cl^- reduces the passive current substantially. All the alloys contain a large amount of a primary aluminium-rich phase which is preferentially corroded and the corrosion behaviour of the alloys reflects the behaviour of the aluminium-rich phase.     

Environmental factors affecting the corrosion behavior of reinforcing steel II. Role of some anions in the initiation and inhibition of pitting corrosion of steel in Ca(OH)2 solutions

Potential-time curves are constructed for the steel electrode in naturally aerated Ca(OH)₂ solutions simulating the corrosion behavior in concrete. Cl⁻ and SO₄²⁻ ions cause the destruction of passivity and initiation of pitting corrosion. The rate of oxide film growth by Ca(OH)₂ and oxide film destruction by Cl⁻ and SO₄²⁻ ions follows a direct logarithmic law as evident from the linear relationships between the open-circuit potential and the logarithm of immersion time. Chromate, phosphate, nitrite, tungstate and molybdate ions inhibit the pitting corrosion of steel. The rate of oxide film healing and thickening increases with their concentrations. In presence of constant inhibitor concentration, the efficiency of pitting inhibition increases in the order: (weak) CrO₄²⁻ < HPO₄²⁻ < NO₂⁻ < WO₄²⁻ < MoO₄²⁻ (strong).     

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.     

Effect of calcium ions on pitting corrosion and inhibition performance in CO2 corrosion of N80 steel

The electrochemical impedance spectroscopy (EIS) and polarization resistance technique were used to investigate the susceptibility of N80 steel to pitting corrosion under stagnant condition and the corrosion behavior under flowing condition with/without precorrosion in 3% NaCl solution, in 3% NaCl + 1.5% CaCl₂ solution and in 4.6% NaCl solution (equivalent Cl⁻ concentration to 3% NaCl + 1.5% CaCl₂ solution) saturated by CO₂ at 57 °C. The results showed that under stagnant condition the initiation period of pitting corrosion decreased with increasing Cl⁻ concentration, but at the same Cl⁻ concentration, Ca²⁺ could prolong the initiation period. Under flowing condition the corrosion rate without stagnant precorrosion was bigger than that with precorrosion, and the corrosion rate with precorrosion in 3% NaCl solution was bigger than that in 3% NaCl + 1.5% CaCl₂ solution. Inhibition of quaternary alkynoxymethyl amine (IMC-80-Q) under stagnant condition showed that the optimum inhibitor concentration significantly increased with the increase of Cl⁻ concentration from 3% NaCl solution to 4.6% NaCl solution, and for the solutions with the same Cl⁻ concentration, adding Ca²⁺ did not change the optimum inhibitor concentration.     

Influence of N,N′‐dimethylaminoethanol as an inhibitor on the chloride threshold level for corrosion of steel reinforcement

The aim of this study is to examine the influence of N,N′‐dimethylaminoethanol (DMEA) as an inhibitor on the chloride threshold level for corrosion of steel in a concrete contaminated by chlorides. The experiment has been carried out in a saturated Ca(OH)₂ solution and chloride contaminated concrete containing different chloride and DMEA level. The critical point of corrosion onset is concluded by combining the open‐circuit potential (E_corr) with corrosion current (I_corr), which is decided by electrochemical impedance spectra (EIS) in the solution. Besides, the EIS has also been applied to determinate the chloride threshold level in the chloride contaminated concrete. It has been found that the presence of DMEA represented as an amino‐alcohol inhibitor, exerts little influence on the chloride threshold level for corrosion of steel in the solution. Similarly, the effect of the DMEA on the chloride threshold level in the chloride contaminated concrete, is also negligible.     

Effect of common water contaminants on the corrosion of aluminium alloys in ethylene glycol-water solution

The effects of common water contaminants of chloride (Cl⁻), cupric (Cu²⁺) and ferric (Fe³⁺) ions, in four different mixture combination of Fe³⁺ + Cu²⁺, Cl⁻ + Fe³⁺, Cl⁻ + Cu²⁺ and Cl⁻ + Fe³⁺ + Cu²⁺, were examined on the corrosion behaviour of aluminium alloys in ethylene glycol-water solution, using mass loss technique. The highest material losses were recorded for the two alloys in ethylene glycol solution containing the combination of the chloride and the two heavy metal ions. The corrosivity of the solution in the presence of the combination of ions was in the order of Cl⁻ + Fe³⁺ + Cu²⁺ > Cl⁻ + Cu²⁺ > Cl⁻ + Fe³⁺ > Fe³⁺ + Cu²⁺. The results gave first-order kinetics with respect to aluminium in ethylene glycol solution-ion systems. Alloy 3SR exhibits maximum corrosion in all the solutions. It is concluded that the two commercial alloys in the solution polluted with all the three ions would not be able to survive for reasonable period of time without corrosion inhibitor.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

Corrosion behaviour of low-carbon bainitic steel under a constant elastic load

The corrosion behaviour of low-carbon bainitic weathering steel in an environment containing chlorine ions (Cl⁻) was studied by applying different constant elastic loads. The results showed that the applied elastic load reduces the resistance of the rust layer to Cl⁻ diffusion because of the porous structure as well as the enhanced anion selectivity in the rust: this leads to more severe corrosion of the steel compared with load-free conditions. The corrosion rate increased with increasing loads. Corrosion enhancement can be attributed to mechanical-chemical interactions at the steel surface.     

Influence of pH on the nitrite corrosion inhibition of reinforcing steel in simulated concrete pore solution

Measurements of corrosion rate of reinforcing steels have been carried out in solutions simulating electrolytic chloride environments in corrosion pits in the propagation period with sodium nitrite. A significant corrosion inhibition has been observed at relatively low chloride contents of 0.045 M due to the presence of nitrite in these systems, but its efficiency decreases when the pH is reduced. The corrosion intensity seems to be related to the [Cl⁻]/[OH⁻] ratio. Three different pH regions from acid to alkaline have been observed in terms of corrosion activity. An explanation on the behaviour of nitrite at different pH is given.     

Effectiveness of pretreatment method to hinder rebar corrosion in concrete

Abstract

This paper aims to evaluate the ability of phosphate pretreatments applied on steel rebars to hinder the corrosion reinforcements using synthetic pore electrolyte and mortar contaminated by chloride ions. The electrochemical behaviour of the pretreated substrate was assessed by corrosion potential, polarisation resistance and electrochemical impedance spectroscopy measurements. The results have demonstrated that the treatment of the rebar by immersion in the Na₃PO₄ (0·5M) solution favours the formation of a passive layer on the steel rebar surface, which increases the resistance to corrosion initiation up to 0·3M Cl^– instead of 0·1M Cl^– without treatment. The pretreatment also provides enhancement of corrosion protection of the steel rebar in mortar. The evolution of the impedance spectra in function of chloride concentration is in a fairly good agreement with the results obtained from R_P measurements.     

Pit to crack transition in stress corrosion cracking of a steam turbine disc steel

Long term exposure tests have been carried out on a 3 NiCrMoV steam turbine disc steel in the form of cylindrical tensile test specimens self-loaded to 90% of σ_0.2 and exposed to three environmental conditions, viz. deaerated pure water, aerated pure water, and aerated water containing 1.5 ppm of chloride ion. Pitting occurred in all environments but the density and depth of pits in the chloride-containing medium was markedly greater. No cracking was observed in deaerated pure water but cracks initiated in aerated water between 13 and 19 months and in less than 7 months in aerated 1.5 ppm Cl⁻ solution. The probability of a crack initiating from a pit of specific depth in aerated solution could be described well by a Weibull function. Profiling of pits and cracks in the disc steel tested in aerated 1.5 ppm Cl⁻ solution showed that there while there were many cracks with a depth greater than that of the corresponding pit the depth of some cracks was smaller than that of the corresponding pit, suggesting that cracks do not necessarily initiate from the bottom of the pits. The growth rate of short cracks emerging from pits appeared greater than that of long cracks in fracture mechanics specimens.