Corrosion protection of steel reinforcement by a pretreatment in phosphate solutions: assessment of passivity by electrochemical techniques

Abstract

The aim of this work is to study the protection of steel reinforcement against corrosion by pretreatment in phosphate (Na₃PO₄) solution. The work has been carried out using electrochemical techniques, i.e. corrosion potential E _corr, polarisation resistance R _P and electrochemical impedance spectroscopy (EIS) measurements. The results have been validated by a gravimetric method. It has been stressed that R _P measurements, determined by DC techniques, include the charge transfer resistance R _t plus the resistance associated with the redox process R _ox, both determined by EIS. Also 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 is able to resist longer the action of chlorides to initiate corrosion. However, the resistance of the passive layer against chloride depends on the duration of the treatment by immersion of the rebar within the phosphate solution.     

Depassivation of steel reinforcement in case of pitting corrosion: detection techniques for laboratory studies

Methods for service life prediction of reinforced concrete structures exposed to chloride‐bearing environments require, amongst other parameters, the knowledge of the chloride threshold for pitting corrosion initiation (Cl_th). Nowadays, although the main factors influencing the chloride threshold are well known, it is often difficult to quantify a value of the chloride threshold, partly because of its intrinsic high variability, and partly because of the different test methods that have been used to measure it. All the experimental tests rely on the detection of steel depassivation and simultaneous measurement of chloride content or steel potential. This paper deals with the methods that can be used to detect steel depassivation in relation with the determination of the chloride threshold. Tests in concrete‐pore‐simulating solutions as well as tests in concrete will be considered, and advantages and limitations will be discussed.     

The use of electrochemical techniques for the investigation and monitoring of microbiologically influenced corrosion and its inhibition – a review

The background of several electrochemical techniques – recording of the corrosion potential E_corr, electrochemical impedance spectroscopy (EIS), electrochemical noise analysis (ENA) and recording of potentiodynamic polarization curves – has been discussed and examples of the use of these techniques in studies of microbiologically influenced corrosion (MIC) and MIC inhibition have been presented. These examples range from the use of the polarization resistance R_p and the noise resistance R_n in corrosion monitoring in a sewer environment and a gas production field, respectively, to the application of EIS and ENA in the evaluation of the interaction of bacteria with protective coatings on steel exposed to natural seawater (NS). A more detailed analysis based on EIS and ENA of Corrosion protection of Al 2024, mild steel and brass in artificial seawater (AS) by bacteria such as B. subtilis, B. licheniformis, E. coli and Shewanella has been presented. Determination of the changes of R_p and R_n as well as E_corr allows to propose appropriate mechanisms of MIC inhibition. These mechanisms have been confirmed in the case of S. algae by recording of anodic and cathodic potentiodynamic polarization curves after exposure to AS containing the bacteria for extended time periods.     

Initial corrosion protection of Zn–Mn alloys electrodeposited from alkaline solution

The effects of a deposition current density (c.d.) on the corrosion behaviour of Zn–Mn alloy coatings, deposited from alkaline pyrophosphate solution, were investigated by atomic absorption spectrophotometry (AAS), X-ray diffraction (XRD), atomic force microscopy (AFM), optical microscopy, electrochemical impedance spectroscopy (EIS) and measurement of corrosion potential (E_corr). XRD analysis disclosed that zinc hydroxide chloride was the main corrosion product on Zn–Mn coatings immersed in 0.5 mol dm⁻³ NaCl solution. EIS investigations revealed that less porous protective layer was produced on the alloy coating deposited at c.d. of 30 mA cm⁻² as compared to that deposited at 80 mA cm⁻².     

Application of harmonic analysis in measuring the corrosion rate of rebar in concrete

The corrosion rate (CR) of rebar embedded in cement mortar, concrete and cement extract is determined using harmonic analysis technique (HA). Simultaneously using other electrochemical techniques such as impedance spectroscopy (EIS) and Tafel extrapolation (TET), the CR was determined and compared with the weight loss method. CR obtained from HA is comparable to that of EIS provided that the Stern–Geary constant (B value) obtained from HA is used in the calculation. In concrete, comparable corrosion rates are obtained between TET and HA only under active condition of the rebar whereas under passive state, the corrosion current (i_corr) by TET is 10 times lower than that of HA. A good agreement is obtained between the HA and weight loss method. The outcome of the result suggests that HA is capable of providing a higher degree of accuracy than that of EIS and TET in the determination of i_corr in the medium like rebar in concrete having very low rate of corrosion.     

Corrosion resistance of low‐nickel duplex stainless steel rebars

The use of stainless steel bars in reinforced concrete structures may be an effective method to prevent corrosion in aggressive environments where high amounts of chlorides may penetrate in the concrete cover. For an estimation of the service life of structures where stainless steel bars are used, the chloride threshold for these rebars should be defined, and the influence of chemical composition and metallurgical factors that may affect the corrosion resistance (strengthening, welding, etc.) should be assessed. To reduce the cost of stainless steel reinforcement, duplex stainless steels with low nickel content have been recently proposed as an alternative to traditional austenitic steels, even though, few results are available regarding their corrosion performance in chloride contaminated concrete. This paper deals with the corrosion resistance of low‐nickel duplex stainless steel rebars (1.4362 and 1.4162) as a function of the chloride content. Comparison is made with traditional austenitic steels. An attempt to define a chloride threshold for the different stainless steels is made by comparing the results of several test procedures both in concrete and in solution.     

Water soluble conducting polymer composite of polyvinyl alcohol and leucine: An effective acid corrosion inhibitor for mild steel

A new corrosion inhibitor namely poly(vinyl alcohol‐leucine) composite (PVAL) has been synthesized and its influence on corrosion inhibition of mild steel in 1 M hydrochloric acid solution has been studied by weight loss and potentiodynamic polarization techniques. The composite (PVAL) showed more than 95% inhibition efficiency (IE) at an optimum concentration of 0.6% by weight. The inhibition efficiency of inhibitor has been found to vary with inhibitor concentration, solution temperature, and immersion time. Various kinetic and thermodynamic parameters (E_a, ΔH_o, ΔS_o for corrosion and ΔG_ads, ΔH_ads, ΔS_ads for adsorption) reveal a strong interaction between inhibitor and mild steel surface. The negative values of ΔG_ads indicate the spontaneous adsorption of the inhibitor on mild steel surface. Potentiodynamic polarization studies showed PVAL as mixed type inhibitor. It inhibits mild steel corrosion by blocking the active sites of the metal. Electrochemical impedance spectroscopic (EIS) techniques were also used to investigate the mechanism of corrosion inhibition.     

Corrosion characterization of microarc oxidation coatings formed on Mg–7Li alloy

Ceramic coatings with thickness of 27 µm were fabricated on Mg–7Li alloy in Na₂SiO₃–C₆H₁₈O₂₄P₆ solution by microarc oxidation (MAO). The morphology and phase composition of MAO coatings were characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The corrosion behavior of the bare and MAO coated Mg–7Li alloy was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Results showed that the MAO coatings were composed of MgO, Li₂O, and Mg₂SiO₄, and there existed some micropores on the coating surface with a diameter of 3–20 µm. The corrosion potential (E_corr) and corrosion current density (I_corr) of the MAO coated alloy were about ?1.4761 V and 7.204 × 10^?7 A/cm², respectively. The E_corr of the MAO coated alloy increased by 109.6 mV and its I_corr decreased by three orders compared with that of the bare Mg–7Li alloy. The EIS plots indicated that the impedance of the MAO coated alloy was 15 times higher than that of the bare alloy. The fitting parameters showed that the resistance of the MAO coatings was far greater than that of the bare alloy. The dense intermediate layer and the transition layer of the MAO coatings acted as a barrier to hinder the proceeding of solution permeation, remarkably improving the corrosion resistance of the Mg–7Li alloy.     

On the corrosion behaviour of phosphoric irons in simulated concrete pore solution

The corrosion behaviour of three phosphoric irons P₁ (Fe-0.11P-0.028C), P₂ (Fe-0.32P-0.026C) and P₃ (Fe-0.49P-0.022C) has been studied in simulated concrete pore solution (saturated Ca(OH)₂ solution) containing different chloride concentration. This has been compared with that of two commercial concrete reinforcement steels, a low carbon steel TN (Fe-0.148C-0.542Mn-0.128Si) and a microalloyed corrosion resistant steel CS (Fe-0.151C-0.088P-0.197Si-0.149Cr-0.417Cu). The beneficial aspect of phosphoric irons was revealed from potentiodynamic polarization experiments. The pitting potentials and pitting nucleation resistances for phosphoric irons and CS were higher than that for TN. Electrochemical impedance spectroscopy (EIS) studies revealed thickening and growth of passive film as a function of time in case of phosphoric irons and CS in saturated Ca(OH)₂ pore solutions without chloride and in the same solution with 0.05% Cl⁻ and 0.1% Cl⁻. In case of TN, breakdown of passive film resulted in active corrosion in simulated pore solution containing 0.1% Cl⁻. Linear polarization resistance measurements complemented EIS results. Visual observations indicated that phosphoric iron P₃ was immune to corrosion even after 125 days of immersion in saturated Ca(OH)₂ solution containing 5% NaCl. The good corrosion resistance of phosphoric irons in simulated concrete pore solution containing chloride ions has been related to the formation of phosphate, based on ultraviolet spectrophotometric analysis and Pourbaix diagram of phosphorus-water system.     

Corrosion behavior of API 5L X‐60 pipeline steel exposed to near‐neutral pH soil simulating solution

Steel gas pipelines are exposed externally to damage by surface corrosion and cracking phenomena. They are the main deterioration mechanism under coating failure and cathodic protection (CP) that can reduce the structural integrity of buried gas transmission pipelines where the soil aggressiveness and bacterial activity appear. Corrosion phenomenon is accentuated by the soil parameters influence such resistivity, pH, temperature, moisture content and chemical composition of electrolytes contained in the soil. Soil parameters influence on pipeline steel corrosion behaviour exposed in near‐neutral pH soil simulating solution has been investigated by potentiodynamic polarisation and EIS method. Results showed that the steel corrosion increases, corrosion current density increases with temperature in the range from 20 to 60 °C. The associated activation energy has been determined. Impedance curves showed that the charge transfer resistance (R_t) increases with increasing immersion duration. Parameters such as corrosion current density (I_corr), polarization resistance (R_p), and soil resistivity (ρ) can serve as the parameters for evaluation of soil corrosivity.     

Preventing or accelerating galvanic corrosion through the application of a proper external magnetic field

The effect of an external magnetic field on the corrosion behaviour of a galvanic couple, zinc (Zn)–stainless steel (SS 316L), has been investigated in a 0·055 mol L^?1 potassium chloride (KCl) solution. The impact of the orientation as well as the magnetic flux density B (Wb m^?2) on the corrosion progression of the galvanic couple, is evaluated heuristically by monitoring the corrosion potential E_corr (mV) and the current density I_corr (μA cm^?2) of the system. A strong influence of the magnitude and orientation of the magnetic field on the Zn–SS316L galvanic couple corrosion was observed, whereas the field was proven to act either protective or accelerating in terms of corrosion.     

The inhibitive effect of 5‐amino‐indole on the corrosion of mild steel in acidic media

The inhibitor performance of 5‐aminoindole (5‐AI) on mild steel corrosion in 0.5 M HCl was investigated in relation to the inhibitor concentration using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and linear polarization (LPR) methods. The effect of immersion time on the corrosion behavior of mild steel was also studied. The impedance data obtained were fitted and modeled using an equivalent circuit model. The results show that 5‐AI is an effective inhibitor and has an inhibition efficiency of 90% at 1 × 10^?2 M additive concentration. The adsorption behavior of 5‐AI was also investigated. For this purpose, the adsorption equilibrium constant (K_ads), and the free energy of adsorption (ΔG_ads) were calculated and discussed. It was found that 5‐AI acts as mixed‐type inhibitor and obeys Langmuir adsorption isotherm with a free energy of adsorption of ?27.71 kJ/mol.     

Detection and identification of concrete cracking during corrosion of reinforced concrete by acoustic emission coupled to the electrochemical techniques

The tenacious oxide passive film, which is formed on the surface of embedded reinforcing steel under high alkaline condition of concrete, protects the steel against corrosion. However, the condition of passivity may be destroyed, due to processes such as leaking out of fluids from concrete, atmospheric carbonation or through the uptake of chloride ions. Passive steel reinforcing corrosion induced by chloride is a well-known problem, especially where chloride-containing admixtures or chloride contaminated aggregate are incorporated into the concrete. The objective of this work is on one hand to study the effect of chloride ions on passivity breakdown of steel, respectively, in simulated concrete pore solution (SCP) and in concrete reinforcement, and on the other hand to reproduce the carbonation phenomena by applying to the concrete samples a heating–cooling cycles. In this context, the acoustic emission coupled to the electrochemical techniques (potentiodynamic and electrochemical impedance spectroscopy (EIS)) are used.

The results show clearly that [Cl⁻]/[OH⁻] ratio of 0.6 is the critical threshold where the depassivation set-up can be initiated. In addition, the carbonation process is very aggressive with chloride ions and shows a perfect correlation with acoustic emission evolution.

A physical model of the reinforcement/electrolyte interface is proposed to describe the behavior of the reinforcement against corrosion in chloride solution.     

Untersuchungen zum kritischen korrosionsauslösenden Chloridgehalt von Stahlfasern in künstlicher Betonporenlösung

Investigations into the critical corrosion‐inducing chloride content of steel fibres in artificial concrete pore solution It is well known, that reinforcement steel in concrete is normally protected against corrosion due to the high pH‐value of the pore solution of the concrete. This alkalinity leads to a passive layer on the steel surface, which prevents further corrosion. The passive layer can be destroyed by chloride ions diffusing into the concrete. The concentration of chloride in the concrete which leads to a destruction of the passive layer and therefore to corrosion of the steel is defined as the critical chloride content. Investigations in artificial concrete pore solutions show that the critical chloride content of black steel is strongly dependent on the pH‐value of the solution: the higher the concentration of the OH⁻‐ions the higher the critical chloride content. For steel fibres earlier investigations have shown, that steel fibres do not corrode in concrete even at high chloride contents. Therefore it could be assumed, that the critical corrosion‐inducing chloride content of steel fibres in concrete is distinctly higher than of conventional reinforcing steel. To verify this assumption the corrosion‐inducing chloride content of steel fibres is investigated in artificial chloride‐containing concrete pore solutions at different pH‐values. 5 different types of steel fibres, 1 lashing wire and as reference 1 reinforcing steel are investigated at 3 different pH‐value ranges. The concentration of chloride within the pore solution is gradually increased in time steps of 12 h. The beginning of corrosion is determined by current as well as potential measurements. Furthermore additional investigations are carried out with intermediate products of the fibre production (steel wires with different diameters) to investigate if the critical chloride content of the wires is increasing gradually with decreasing diameter. The investigations show, that steel fibres in artificial chloride‐containing pore solutions indicate an distinctly increased resistance against chloride‐inducing corrosion compared with conventional reinforcing steel for high pH‐values. With decreasing diameter of wires the critical chloride content increases gradually.     

Über den Einfluß verschiedener Chloridionenkonzentrationen auf die Aktiv-Passiv-Korrosionsempfindlichkeit von Stahl in gesättigter Kalziumhydroxidlösung

Influence of various chloride ion concentrations on the active-passive corrosion susceptibility of steel in saturated calcium hydroxide solution The corrosion of steel in concrete is caused mainly by the presence of chlorides. This effect was investigated by measuring potentiodynamic current-voltage-curves and by potentiostatic experiments of stressed (55 or 77% σ_B) plain steel electrodes in saturated Ca(OH)₂-solution with varying chloride concentrations. The results show that down to Cl′-concentrations of 100 mg/l there is a significant statistical probability of corrosion within 48 hours, and that for longer times the threshold concentration may be even lower. The microscopical examination of corroded samples shows that under the experimental conditions only pitting corrosion is the cause of failure and that this pitting is promoted by the applied stress.     

Investigations of an ethanolamine‐based corrosion inhibitor system for surface treatment of reinforced concrete

Laboratory investigations were performed to assess the efficacy of a proprietary ethanolamine‐based corrosion inhibitor system when applied to the surface of reinforced concrete specimens that were chloride‐contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately eighteen months thereafter. Gravimetric measurements of the quantities and distribution of corrosion on the steel were also made on completion of the exposure tests. Analysis of aqueous extracts from treated concrete revealed that the ethanolamine component of the inhibitor system penetrated to depths of more than 15 mm within the concrete. It was found that, for inhibitor‐treated specimens, there was some reduction in the corrosion rate of pre‐corroding steel at low cover depths in non‐carbonated concrete with modest levels of chloride contamination. At higher levels of chloride contamination and in carbonated specimens, however, the ethanolamine‐based inhibitor was apparently ineffective under the conditions investigated.     

The corrosion inhibitory property of N,N‐bis(2‐benzimidazolylmethyl)amine for Q235 steel

The main purpose of this paper is to systematically evaluate the anti‐corrosion property of N,N‐bis(2‐benzimidazolylmethyl)amine (IDB), which is a novel good thermal stabilized inhibitor in acidic medium. Results obtained from electrochemical tests and corrosion surface morphology analyses reveal that IDB performs excellently as corrosion inhibitor for Q235 steel in 1 mol/L hydrochloric acid corrosive solution. Potentiodynamic polarization measurements show that IDB inhibits both the anodic and cathodic processes of corrosion and exhibits as a mixed‐type inhibitor. Besides, the inhibiting efficiency (IE%) and consequently the degree of surface coverage (θ) increase with the inhibitor concentration rising. And when the concentration is 20 × 10^?5 mol/L, the corrosion inhibition effect is best to reach 96.39%. The adsorption of inhibitor on Q235 steel is found to obey the Langmuir adsorption isotherm, and the calculated Gibbs free energy demonstrates that IDB spontaneously adsorbs and forms a protective chemisorbed film on Q235 steel to restrain its corrosion. Hereby, IDB will become a promising corrosion inhibitor in further.     

The wet corrosion of Mo and Mo‐Ti alloy thin film – Part IV: The effect of nitriding

A considerable number of detailed investigations have been carried out on the deposition and characterisation of molybdenum and molybdenum‐titanium‐nitride films by employing a variety of techniques. However, very little is currently known about the effect of composition (N₂/Ar flow rate) on the corrosion properties of MoN and MoTiN thin films for aggressive ambient conditions. In this work, the electrochemical and corrosion behaviour of MoN and MoTiN thin films, produced by Physical Vapour Deposition (PVD) with different N₂/Ar flow rates, has been investigated by Electrochemical Impedance Spectroscopy (EIS) in aerated alkaline chloride solution and compared with the behaviour of pure molybdenum in the same environment. Results obtained indicate that increasing nitrogen content in the film leads to a beneficial effect on the corrosion resistance, but results in decreased electrical conductivity of the film that may limit their application as back contact in photovoltaic modules.     

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.     

Corrosion inhibition of mild steel in hydrochloric acid by 6‐aminohexanoic acid

The inhibiting behavior of 6‐aminohexanoic acid (C₆H₁₃NO₂) on mild steel corrosion in 1 M HCl as corroding solution at 25 °C was evaluated by weight loss, polarization, and electrochemical impedance spectroscopy (EIS) methods. The weight loss, polarization, and EIS measurements were relatively in good agreement together. Results obtained by the three methods showed that the inhibition efficiency (%IE) increases with increasing the concentration of 6‐aminohexanoic acid up to 6.86 × 10^?05 M (about %IE = 80). It was also found that the adsorptive behavior of the investigated inhibitor on the steel surface followed Langmuir‐type isotherm, the 6‐aminohexanoic acid acted as a mixed type inhibitor and its inhibition mechanism obeys from the chemisorption interaction between 6‐aminohexanoic acid and the mild steel.