Initiation and repassivation of pitting corrosion of carbon steel in carbonated concrete pore solution

The initiation, propagation, repassivation of metastable pits of Q345 carbon steel in Cl⁻ containing concrete pore solution were studied by electrochemical noise. The initiation rate of metastable pits increases exponentially up to a constant value with time. After stable pit occurs, the nucleation of metastable pits is mainly induced by the rust layer, and mainly takes place in the outskirt of the rust layer. Stable pits incline to expand horizontally to produce a shallow pit. In addition, high concentration of nitrite can inhibit the nucleation of metastable pits around the rust cover and accelerate the repassivation of stable pits.     

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, passivation and breakdown of passivity of neodymium

The anodic polarisation behaviour of neodymium was investigated in various solutions (pH 1-12). While in sulphuric acid solution high dissolution rates were observed, spontaneous passivity occurred in phosphoric acid solutions, oxalic acid solutions and sodium hydroxide solutions. However, the stability of these protecting layers strongly depends on the kind and concentration of anions present, especially in acidic environments. A mechanism of the passive layer breakdown is proposed. During pitting corrosion erosive degradation of the electrode was observed. In all solutions, abnormal hydrogen evolution was observed when neodymium was in the active state during anodic polarisation.     

Inhibition effect of chromate on the passivation and pitting corrosion of a duplex stainless steel in LiBr solutions using electrochemical techniques

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and the presence of chromate in the solutions on the corrosion behavior of AISI 2205 was studied. Cyclic polarization curve analyses showed that there was different pitting susceptibility of passive films depending on the LiBr concentration. Pitting potential decreases with LiBr concentration in a semilogarithmic scale following two different slopes. Chromate presence displaces pitting potentials towards more positive values at low LiBr concentrations but it has no effect when LiBr concentration increases.The comparative analysis carried out in LiBr and LiBr chromate-containing solutions at two different concentrations, 0.016 M and 0.032 M, verifies the assumption that halogen ions facilitate inhibitor adsorption. The addition of halides strongly increased the inhibition efficiency of chromate. The passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

Oxide networks, graph theory, and the passivity of Ni–Cr–Mo ternary alloys

The passivity of Ni–Cr–Mo ternary alloys is considered in terms of a continuous network of –Cr–O–Cr– bridges in the oxide film (which also contains Ni²⁺ and Mo⁴⁺ ions), or in terms of a continuous network of –Ni–O–Ni– bridges in the oxide film (which also contains Cr³⁺ and Mo⁴⁺ ions). The structure of the oxide is represented by a mathematical graph, and graph theory is used to calculate the connectivity of the oxide. This approach shows that a continuous network of –Cr–O–Cr– bridges occurs when the cation fraction of Cr³⁺ ions in the oxide is 0.35 or greater. A continuous network of –Ni–O–Ni– bridges occurs when the cation fraction of Ni²⁺ ions in the oxide is 0.55 or greater. Experimental results support the –Cr–O–Cr– model.     

Ab initio modelling of localized corrosion: Study of the role of surface steps in the interaction of chlorides with passivated nickel surfaces

Periodic DFT calculations have been performed on a (5 3 3)-oriented hydroxylated NiO surface to model the influence of step edges on the adsorption and sub-surface insertion of Cl at the surface of the passive film on nickel. With increasing Cl coverage, substructures of Ni(OH)₂, Ni(OH)Cl or Ni(Cl)₂ composition are formed and detached from the surface, suggesting a major role of the step edges in the Cl adsorption-induced thinning mechanism of the oxide film. The calculated energies show the promoting effect of the adsorption of Cl on the energy of detachment of the substructures. At surface saturation, sub-surface insertion becomes energetically more favourable than adsorption. The results suggest a possible bifurcation from the Cl adsorption-induced oxide thinning mechanism to the penetration-induced mechanism of passivity breakdown at saturation in adsorbed Cl of the step edges.     

Influence of pitting and iron oxide formation during corrosion of carbon steel in unbuffered NaCl solutions

The corrosion evolution over time of a carbon steel rotating disk immersed in aerated NaCl solutions was analyzed using a superposition model. Using this approach, partial polarization curves for iron oxidation and oxygen reduction were synthesized from experimental current-potential data at different corrosion time in order to determine the kinetics parameters, corrosion potential and current density of the underlying anodic and cathodic subprocesses. The distinctive features of the polarization curves are well described in terms of the simplifying assumptions of the model. In particular, the time evolution of the corrosion current density was linked to the morphology of the corroding surface under different NaCl concentrations.     

Structure and water-barrier properties of vanadate-based corrosion inhibitor films

Uniform, crack-free vanadium-based corrosion inhibitor films were grown on aluminum alloy 2024. Neutron and X-ray reflectivity were utilized to investigate the structure, water-barrier properties and speciation of the inhibitor film. The top part of the alloy participates in the formation of vanadate film. The similarity of films prepared from H₂O and D₂O implies the vanadate film is not hydrated. The film has a layered structure with vanadium enriched at the alloy interface. The film behaves as an effective water barrier when the thickness is greater than 800 Å. Films grown without K₃Fe[CN]₆ accelerator are found to be extremely thin.     

Influence of long-term ageing in solution containing chloride ions on the passivity and the corrosion resistance of duplex stainless steels

The influence of long-term ageing in NaCl on the passivity and the electrochemical behavior of UNS S32304 is studied. The passive film thickness, the Cr/Fe ratio and the chloride content were significantly increased after ageing. The chloride distribution depends on residual stresses, sample microstructure and surface preparation. Local electrochemical measurements revealed that pitting potentials are between 250–550 mV vs. SCE after electropolishing. The higher the chloride content, the lower the local pitting potential. It was also shown that the presence of chloride was balanced by the enrichment in chromium after ageing. Then no pitting potential could be measured.     

Stochastic modeling of pitting corrosion: A new model for initiation and growth of multiple corrosion pits

In this work, a new stochastic model capable of simulating pitting corrosion is developed and validated. Pitting corrosion is modeled as the combination of two stochastic processes: pit initiation and pit growth. Pit generation is modeled as a nonhomogeneous Poisson process, in which induction time for pit initiation is simulated as the realization of a Weibull process. In this way, the exponential and Weibull distributions can be considered as the possible distributions for pit initiation time. Pit growth is simulated using a nonhomogeneous Markov process. Extreme value statistics is used to find the distribution of maximum pit depths resulting from the combination of the initiation and growth processes for multiple pits. The proposed model is validated using several published experiments on pitting corrosion. It is capable of reproducing the experimental observations with higher quality than the stochastic models available in the literature for pitting corrosion.     

Environmental factors affecting the corrosion behaviour of reinforcing steel: I. The early stage of passive film formation in Ca(OH)2 solutions

Oxide film thickening on reinforcement steel at early stage of formation is followed in naturally aerated Ca(OH)₂ solutions, recalling the natural behaviour in concrete, by measuring the open-circuit potential, E, with time up to 4 h. The final potentials, E_fin, are reached from negative values indicating oxide film growth. E varies with the Ca(OH)₂ concentration according to a straight line relationship. Oxide film thickening, at early stage of immersion, follows a direct logarithmic growth law as evident from the linear relationship between E and log t. The rate of oxide film thickening deceases by increasing the concentration and pH of the solution and by raising the temperature. The free activation energy of oxide film thickening is determined and found to be 29.28 kJ/mole, indicating that the process of oxide film growth is under diffusion control.     

Voltammetric current oscillations due to general and pitting corrosion of tantalum: Implications for electrochemical-mechanical planarization

Anodic corrosion of Ta is examined for potential applications in electrochemical-mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of (or Br⁻) to form mechanically weak surface-oxide films, followed by mechanical removal of the latter. The voltammetric currents exhibit oscillatory behaviour with frequencies that are signature attributes of localised pitting by Br⁻ or general surface corrosion by . SEM, voltammetry, and impedance spectroscopy are used to probe these corrosion mechanisms. Apart from their relevance for ECMP, the results also address certain fundamental aspects of pitting and general corrosion of valve metals.     

A model to predict the evolution of pitting corrosion and the pit-to-crack transition incorporating statistically distributed input parameters

A model based on deterministic equations with statistically distributed input parameters has been developed for simulating the evolution of the pit depth distribution at different exposure times and the percentage of pits that transform to stress corrosion cracks. The model has been applied to the specific case of steam turbine disc steel exposed to a range of environments under applied stress. With preliminary fitting at one exposure time, the simulation not only reflects the trends in the experimental measurement but also the model, uniquely, reproduces the statistical variability or “noise” associated with the measurements.     

A comparative H2S corrosion study of 304L and 316L stainless steels in acidic media

H₂S corrosion of 304L and 316L in oxygen-free Na₂SO₄ + Na₂S solution at pH 3 and temperature of 60 °C were investigated by EIS, potentiodynamic polarisation, multi-component Pourbaix diagrams and microstructure characterization. At similar conditions, lower corrosion rate was observed on 316L, attributed to its denser (1.5 times) and smoother (6%) surface layer and confirmed by SEM micrograph. During polarisation, H₂S increases significantly the critical current density on 304L and passivation current density, i_p, on 316L. Higher i_p on 316L was associated to simultaneous FeS₂–MoS₂ preservation, confirmed by XRD examination. H₂S could have an inhibiting effect on 304L in passivity region.     

Solubilisation of nickel from powders at near-neutral pH and the role of oxide layers

Dissolution rates of nickel powder in pH 5 acetate buffers were observed to be an effective indicator of the thickness of the oxide layer on the surface of the nickel particle. Tests on powders pre-cleaned with acid or pre-oxidized in air demonstrated this dependence. The saturation level of nickel in the solution is not greatly affected by the initial state of the powder. Effects of additive solutes are most pronounced during short-term dissolution tests. Among such solutes, reduced sulphur and selenium species, phosphate, fluoride, oxalate, and permanganate cause the largest increases in dissolution rate, while hexacyanoferrate, arsenite, periodate, chromate, vanadate, molybdate, iodate, and tungstate suppress the dissolution.     

A study on the localized corrosion of cobalt in bicarbonate solutions containing halide ions

The localized attack of cobalt in bicarbonate aqueous solutions containing halide ions was investigated using electrochemical techniques, scanning electron microscopy, UV-visible and Raman spectroscopies. Rotating disc and rotating ring-disc electrodes were used to determine the effect of bicarbonate concentration, solution pH, nature and concentration of the halide ions, convection and potential sweep rate on the corrosion processes. These parameters were found to play a key role on the localized attack induced by halide ions by influencing the production of a Co(HCO₃)₂ precipitate on the pit surface. Potentiostatically generated cobalt oxide films (CoO and Co₃O₄) were found to be efficient to reduce pitting corrosion of cobalt.     

Identifying the role of nanoscale heterogeneities in pitting behaviour of Al-based metallic glass

To clarify the correlation of nanoscale heterogeneity with corrosion in Al-based metallic glasses, three model alloys with a single nanoscale α-Al, Al₃Ni or Al₁₁Ce₃ phase embedded in amorphous Al-Ni-Ce alloy matrix were obtained directly by melt quenching. The results indicated that the high pitting corrosion resistance of AM alloys was not deteriorated by nanocrystalline α-Al precipitation; whereas the pitting potential was slightly decreased and considerably reduced relative to their amorphous state due to the precipitation of nanocrystalline Al₃Ni or Al₁₁Ce₃ respectively. Such a pitting sensitivity of different types of heterogeneities attributes to the nano-scale pit initiation events.     

Evaluation of the corrosion protection behaviour of poly(neutral red) films on passivated copper

The corrosion protection behaviour of poly(neutral red) (PNR) films on copper electrodes has been investigated using open circuit measurements, Tafel plots and electrochemical impedance spectroscopy. Pure copper electrodes were initially passivated in sodium oxalate, salicylate or hydrogen carbonate solution, to inhibit copper dissolution at potentials where neutral red monomer oxidation occurs, before its electropolymerization by potential cycling. The corrosion inhibition by these films was tested in 0.10 M KCl solution. It was found that, after long immersion times (96 h), the best protection efficiency was with PNR films formed on copper passivated in oxalate solution.     

Localized attack of copper and brass in tap water: the effect of Pseudomonas

The presence of Pseudomonas fluorescens in artificial tap water (ATW) affects the composition of the oxide layer and the susceptibility to pitting corrosion of copper and 70/30 brass. The surface layer was investigated by means of a combination of electrochemical and spectroelectrochemical techniques involving cyclic voltammograms, potentiodynamic reduction curves, anodic polarisation curves, weight-loss tests and reflectance spectroscopy.In the sterile conditions the mass loss is lower in brass than in copper while the presence of bacteria enhances the attack in brass. Dezincification in inoculated electrolyte was revealed by microscopic observation, as well as by potentiodynamic reduction curves. Zn dissolution was also supported by spectroscopic evidence.Slow-rate voltamperometric curves were used to determine potential values characteristic of localized corrosion. In the presence of bacteria, the pitting potential moves towards more positive values for both materials but the difference between the repassivation and the pitting potential increases. Bigger and deeper pits can be seen in the presence of microorganisms.     

Critical pitting temperature (CPT) assessment of 2205 duplex stainless steel in 0.1 M NaCl at various molybdate concentrations

In this study, the influence of various concentrations of molybdate () on critical pitting temperature (CPT) of duplex stainless steel 2205 (DSS 2205) in 0.1 M NaCl solution has been investigated by employing potentiodynamic and potentiostatic CPT measurements methods. No significant increase in CPT was observed in the presence of 0.0001 and 0.001 M molybdate. However, addition of 0.01 M increases 10 °C in CPT and pitting corrosion was not observed in solution containing 0.1 M molybdate up to 85 °C. Potentiostatic CPT measurements showed CPT values of 68 and more than 85 °C in 0.01 and 0.1 M molybdate concentrations, respectively.