Untersuchungen über die Lochfraßkorrosion des passiven Eisens in chlorionenhaltiger Schwefelsäure

Investigation into pitting corrosion of passive iron in sulphuric acid containing chloride ions Pitting corrosion of metallic materials is generally connected with presence of a surface layer giving rise to a local differentiation of the electrochemical behaviour of the metal surface. The pitting corrosion by halogen ions on passive metals is investigated using passive iron in chloride ion-containing sulphuric acid as the model system. Quantitative data are presented concerning the mechanism and kinetics of the individual processes giving rise to pitting corrosion in a chloride ion concentration range covering three powers of ten, and in the whole potential range of iron passivity, from the Flade potential to the transpassive breakthrough potential. Pit formation normally follows a linear kinetic law, the rate depending in particular from the chloride ion concentration and from the thickness of the passive layer. The growth of pit diameters follows a linear kinetic law, too; the dissolution current density in the pits depends from the chloride ion concentration. Comparative investigations carried out on active iron, and potential distribution as measured in the pits show that the metal is active in the pits, too. The heterogeneous mixed electrode condition — active pit/passive metal surface — is stabilised by resistance polarisation. The investigations so far do not permit any statement concerning the specific effect of the chloride ions.     

Sequence of steps in the pitting of aluminum by chloride ions

Corrosion pit initiation in chloride solutions is given by an electrode kinetic model which takes into account adsorption of chloride ions on the oxide surface, penetration of chloride ions through the oxide film, and localized dissolution of aluminum at the metal/oxide interface in consecutive one-electron transfer reactions. A previous model has been extended here to consider that penetration of chloride ions can occur by oxide film dissolution as well as by migration through oxygen vacancies. Pit initiation occurs by chloride-assisted localized dissolution at the oxide/metal interface. The electrode kinetic model leads to a mathematical expression which shows that the critical pitting potential is a linear function of the logarithm of the chloride concentration (at constant pH), in agreement with experiment. The model also predicts that the critical pitting potential is independent of pH (at constant chloride concentration), also in agreement with experiment. Corrosion pit propagation leads to formation of blisters beneath the oxide film due to localized reactions which produce an acidic localized environment. The blisters subsequently rupture due to the formation of hydrogen gas in the occluded corrosion cell. Calculation of the local pH within a blister from the calculated hydrogen pressure within the blister gives pH values in the range 0.85 to 2.3.     

Growth of corrosion pits on stainless steel in chloride solution containing dilute sulphate

The effects of dilute sulphate on metastable and stable pitting of 304 stainless steel in chloride solution have been studied. The presence of sulphate causes the distribution of available pit sites to be shifted to a higher potential, implying that pit nucleation is inhibited. Pit propagation, in both the metastable and stable states, is also inhibited by the sulphate ion. The reduced pit propagation current densities are described quantitatively with respect to the effect of sulphate on the solubility of the metal cation in the pit anolyte. The results are consistent with the observation that metastable and stable pits grow under diffusion control, at a rate which is independent of electrode potential. Pit nucleation and propagation in stainless steel are two distinct processes, of which only the former is directly affected by the potential.     

Understanding the effects of electrode inhomogeneity and electrochemical heterogeneity on pitting corrosion initiation on bare electrode surfaces

The effects of electrode inhomogeneity (EI) and electrochemical heterogeneity (EH) on pitting corrosion initiation have been analysed by revisiting research findings reported in the literature and experimental evidences obtained in our laboratories using the wire beam electrode (WBE) method. Two mechanisms of pitting corrosion initiation have been identified on bare metal surfaces exposed directly to electrolytes. For WBE surface under free corrosion or low anodic polarisation conditions the initiation of pitting corrosion was found to be due to the disappearance of minor anodes, leading to accelerated dissolution of a few remaining major anodes. The nucleation stage of pitting corrosion appeared to be controlled by EI, while the propagation stage appeared to be determined by EH. For WBE surface under large anodic polarisation the initiation of pitting corrosion was found to be due to the formation of active new anodic sites, which is in agreement with the conventional mechanism of pitting nucleation.     

Über die Koexistenz aktiver und passiver Bereiche auf einer Elektrodenoberfläche. Ein Beitrag zur Theorie der Lochfraßkorrosion

The coexistence of active and passive zones at a blockade If lead is anodically dissolved, under galvanostatic conditions, in a chromate solution, or zinc in a phosphate solution, each containing a conducting salt, active and passive zones will occure concurrently at certain current intensities. The passive zones are formed by a lead chromate or zinc phosphate film. The active zones dissolve very quickly, the passive zones are virtually permanent. As a result, there occurs a kind of pit corrosion at such systems. For the coexistence of active and passive zones, the experiments in agreement with a working thesis, based on the mutual diffusion of metal ions and film-generating anions, show that the density of the dissolution current at the active spots is proportional to the concentration of the film-generating anions in the solution, and inversely proportional to the Nernst diffusion film thickness. With given electrolyte, and constant stirring conditions, the area of the active zones is proportional to the connected anodic current, while the electrode potential (pitting corrosion potential) assumes a value which is independent of the current.     

用随机分析方法研究磁场对纯镁点蚀过程的影响机理

通过恒电位的方法测量了在有无磁场条件下纯镁的电流-时间响应曲线,并用随机的方法对结果进行分析,研究了磁场对纯镁点蚀产生过程和点蚀成长概率的影响。磁场通过洛仑兹力产生磁流体动力学效应（Magnetohydrodynamic）,显著地增加了纯Mg的点蚀敏感性：对于点蚀的产生过程,磁场的存在改变了纯镁的点蚀产生机制。在无磁场作用的条件下,纯镁的点蚀产生过程都遵循“生死异地”的B1机制;在有磁场作用的条件下,纯镁的点蚀产生过程都遵循“相同点蚀并联”的A3机制。磁场不仅增大了点蚀产生速度,而且降低了点蚀的再钝化速度。对于点蚀的成长过程,磁场提高了稳态点蚀的成长概率,更容易成长为较大的点蚀坑。     

Modeling pitting corrosion by means of a 3D discrete stochastic model

Pitting corrosion is difficult to detect, predict and design against. Modeling and simulation can help to increase the knowledge on this phenomenon as well as to make predictions on the initiation and progression of it. A cellular automaton based model describing pitting corrosion is developed based on the main mechanisms behind this phenomenon. Further, a sensitivity analysis is performed in order to get a better insight in the model, after which the information gained from this analysis is employed to estimate the model parameters by means of experimental time series for a metal electrode in contact with different chloride concentrations.     

Localised dissolution of iron in buffered and non-buffered chloride containing solutions

Pitting corrosion of pure iron was studied by using conventional samples, and artificial pit electrodes. Experiments were conducted in solutions of 0.01, 0.1 and 1 mol dm⁻³ NaCl at pH values of 7, 10, 11 and 12; and in borate buffer solutions with the same chloride concentrations and pH 8.7 and 9.2. Four times higher concentration of borate salt was required to reach inhibiting capacity of the hydroxyl anions, as determined via pitting potentials. From measurements of solution resistance, the increase in local conductivity due to dissolved corrosion products exuded from the pit was calculated for each bulk solutions. For the artificial pit electrodes, contribution of the borate species to the internal pit solution conductivity in low chloride solution was associated with the difference between transition potential, E_T, values for buffered and non-buffered solutions, and this contribution was also used to explain the non-linear dependence of E_T on [Cl⁻]. Further analysis was conducted using the concept of the critical i.x parameter for stable pit propagation.     

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.     

Initial stages of corrosion pits on AISI 1040 steel in sulfide solution analyzed by temporal series micrographs coupled with electrochemical techniques

This work presents a study of the initial instants in the pitting corrosion of AISI 1040 steel, analyzed by temporal series micrographs coupled to an open circuit potential (E_oc) and polarization curves. During the E_oc measurement, the pit induction time and the initial pit growth in MnS inclusions was detected in alkaline sulfide solution. The pit area behavior has two distinct rate of area changes in specific regions directly associated to current slope changes. Finally, it was possible to create a three-dimensional model of the pit depth evolution on the metal, using Faraday’s law and the bullet-shaped geometry.     

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.     

SVET, AFM and AES study of pitting corrosion initiated on MnS inclusions by microinjection

As pitting is a random phenomenon, it is difficult to predict where a pit will appear on the surface and consequently the use of local probes is rendered difficult. In this work, a new method to study pitting corrosion on a MnS inclusion on 316L stainless steel is proposed. It consists in modifying locally the chemistry in its vicinity by injecting with a microcapillary an aggressive solution of NaCl, H₂SO₄ or HCl. Once a pit appears, scanning vibrating electrode technique (SVET) is used to follow the current fluctuations over and around the pit when the metal is polarized at a passive potential. In another series of experiments the effect of local activation of MnS inclusion was studied ex-situ using Auger electron spectroscopy (AES) and atomic force microscopy. It is observed that a single pit can be initiated only when hydrochloric acid is injected, whereas sulphuric acid only partially dissolved the inclusion. On another hand, the surface morphology is not affected when a sodium chloride solution is injected. A significant enrichment in sulphur is detected around the inclusion by AES, and micropits are observed in the metal at the edge of the inclusion after HCl activation. Anodic zones are detected by SVET around the inclusion, whereas a cathodic current flows from the inclusion. The anodic current is clearly ascribed to the breakdown of passivity induced by adsorbed sulphur coming from the MnS dissolution, whereas various assumptions can be proposed for the origin of the cathodic current.     

Role of water, acetic acid and chloride on corrosion and pitting behaviour of carbon steel in fuel-grade ethanol

The role of water, acetic acid, chloride, and oxygen level in corrosion and pitting behaviour of carbon steel in simulated fuel-grade ethanol (SFGE) was investigated. In the absence of the supporting electrolyte, modified cell geometry enabled us to conduct the electrochemical measurement in low-conductivity ethanolic solutions. Results have shown that the water in the SFGE strongly influences the surface film stability and interface electrochemistry in ethanolic environments. The increase in the water concentration induces pitting and metal loss. Dissolved chlorides and higher acidity promote the pit initiation and growth. Alkaline condition inhibits both localized and uniform corrosion.     

The corrosion and passivation of iron in the presence of halide ions in aqueous solution

The anodic dissolution behaviour of iron in halide solutions has been studied with both stationary and rotating electrodes. With stationary electrodes active dissolution kinetics are observed, whereas with rotation a pronounced active/passive transition occurs. A distinct pitting potential (E_c) was noted in each solution, the value of E_c increasing in the order I>Br>Cl>F. Halide ion concentration and electrode velocity did not have any effect on the value of E_c, indicating that the kinetics of pit initiation are independent of mass-transfer effects.During anodic dissolution at potentials more regative than E_c, an inhibiting effect was noted, the degree of which depended on the atomic radius of the anion. A model is suggested which involves three electrode reactions of iron with the electrolyte: (1) Active dissolution involving the well-known FeOH⁺ (ads) rate-determining step. (2) Above the passivation potential, increased reaction of the metal surface with hydroxyl ions causes passivation due to the enhanced access of OH^? to the surface and accelerated removal of solvated protons caused by rotation and a thinning of the diffusion layer. (3) At the pitting potential, direct reaction of the metal with electro-adsorbed halide ions produces pit initiation and growth by a complex ion formation reaction not possible at lower electrode potentials.     

The corrosion and passivation of iron in the presence of halide ions in aqueous solution

The anodic dissolution behaviour of iron in halide solutions has been studied with both stationary and rotating electrodes. With stationary electrodes active dissolution kinetics are observed, whereas with rotation a pronounced active/passive transition occurs. A distinct pitting potential (E_c) was noted in each solution, the value of E_c increasing in the order I>Br>Cl>F. Halide ion concentration and electrode velocity did not have any effect on the value of E_c, indicating that the kinetics of pit initiation are independent of mass-transfer effects.During anodic dissolution at potentials more negative than E_c, an inhibiting effect was noted, the degree of which depended on the atomic radius of the anion. A model is suggested which involves three electrode reactions of iron with the electrolyte: (1) Active dissolution involving the well-known FeOH⁺ (ads) rate-determining step. (2) Above the passivation potential, increased reaction of the metal surface with hydroxyl ions causes passivation due to the enhanced access of OH^? to the surface and accelerated removal of solvated protons caused by rotation and a thinning of the diffusion layer. (3) At the pitting potential, direct reaction of the metal with electro-adsorbed halide ions produces pit initiation and growth by a complex ion formation reaction not possible at lower electrode potentials.     

Effect of direct current electric field on atmospheric corrosion behavior of copper under thin electrolyte layer

A thin layer electrochemical cell was successfully developed to study the atmospheric corrosion behavior of copper film in printed circuit board (PCB-Cu) under thin electrolyte layer (TEL) and direct current electric field (DCEF) by electrochemical impedance and electrochemical noise analysis. The electrochemical measurements and SEM morphologies after corrosion test indicate that DCEF decreases the corrosion of PCB-Cu under TEL. The corrosion rate and probability of pitting corrosion of PCB-Cu under DCEF decrease due to the electric migration of aggressive Cl⁻ ion out of working electrode surface.     

Effects of cerium on the compositional variations in and around inclusions and the initiation and propagation of pitting corrosion in hyperduplex stainless steels

Ce addition to a hyperduplex stainless steel increased its resistance to pitting corrosion because of the formation of stable Ce oxides and a decrease in the area of microcrevices between the matrix and inclusions that act as pit initiation sites. In addition, Cr-enriched zones were formed around Ce oxides with low Cr content in the Ce added alloy. Pitting corrosion in the base alloy initiated at the microcrevice and propagated to Cr oxides, which deteriorated the pitting corrosion resistance. However, pitting corrosion in the Ce added alloy propagated not to the stable Ce oxides but to the matrix.     

Real time pit initiation studies on stainless steels: The effect of sulphide inclusions

It has long been accepted that manganese sulphide favours pitting on stainless steels. However, there are different standpoints on the most important mechanism for pit initiation; due to dissolution of sulphide inclusions, chromium depletion around the inclusion or mechanical rupture of the passive film by metal chlorides. Analysing the pitting potential and metastable pitting rates on different grades of stainless steels has rationalised the effect of sulphide content on pitting corrosion resistance. In situ atomic force microscopy (AFM) has been used in conjunction with conventional electrochemical techniques for imaging real time pit initiation events.     

Deterioration in critical pitting temperature of 904L stainless steel by addition of sulfate ions

This paper deals with the effect of adding sulfate on the critical pitting temperature (CPT) of highly alloyed austenitic stainless steel. A large number of potentiodynamic CPT measurements and potentiostatic current-time curves were obtained in 1 M NaCl containing 0, 0.2, 0.5 and 0.75 M Na₂SO₄. Provided the CPT is defined as the first temperature where stable pitting occurs at intermediate potentials, such as 600 mV (Ag/AgCl), addition of sulfate is shown to have the unexpected effect of lowering the CPT. The growing pits formed in sulfate-containing solution passivate anodically as the potential is increased, perhaps via salt precipitation. The effect of sulfate on pitting kinetics was studied using 50 μm-dia. 302SS wire in 1 M NaCl and 1 M NaCl + 0.5 M Na₂SO₄ at 40 °C. Sulfate increases the critical concentration of metal salt in the pit, expressed as a fraction of the saturation concentration, that is required to sustain pit dissolution. Provided this fraction does not exceed 100% of saturation, passivation is enhanced just inside the pit rim, allowing earlier undercutting of the metal surface and a finer pore structure in the lacy metal cover over the pit. The pitting potential measured above the CPT is increased by sulfate addition, but the CPT itself is lowered. Related examples are cited where pitting shows an unusual dependence on some variable such as anion concentration or temperature.     

Pitting corrosion behaviour of austenitic stainless steels - combining effects of Mn and Mo additions

Mn and Mo were introduced in AISI 304 and 316 stainless steel composition to modify their pitting corrosion resistance in chloride-containing media. Corrosion behaviour was investigated using gravimetric tests in 6 wt.% FeCl₃, as well as potentiodynamic and potentiostatic polarization measurements in 3.5 wt.% NaCl. Additionally, the mechanism of the corrosion attack developed on the material surface was analysed by scanning electron microscopy (SEM), X-ray mapping and energy dispersive X-ray (EDX) analysis. The beneficial effect of Mo additions was assigned to Mo⁶⁺ presence within the passive film, rendering it more stable against breakdown caused by attack of aggressive Cl⁻ ions, and to the formation of Mo insoluble compounds in the aggressive pit environment facilitating the pit repassivation. Conversely, Mn additions exerted an opposite effect, mainly due to the presence of MnS inclusions which acted as pitting initiators.