Exploration of the effect of chloride ion concentration and temperature on pitting corrosion of carbon steel in saturated Ca(OH) 2  solution

Sharifi‐Asl, Samin; Mao, Feixiong; Lü, Ping; Kursten, Bruno; Macdonald, Digby D.

doi:10.1016/j.corsci.2015.06.010

Cited by 77 publications

(53 citation statements)

References 53 publications

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“…22,38 The oxidation state of host cation within the barrier layer, χ, is chosen as +3 for all cases, assuming the composition of the barrier layer on 304SS (and Alloy-22), carbon steel (and iron), and aluminum are primarily defective-Cr 2 Table III.…”

Section: Results and Analysis By Numerical Optimizationmentioning

confidence: 99%

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The Kinetics of Nucleation of Metastable Pits on Metal Surfaces: The Point Defect Model and Its Optimization on Data Obtained on Stainless Steel, Carbon Steel, Iron, Aluminum and Alloy-22

Lü

Engelhardt

Kursten

et al. 2016

J. Electrochem. Soc.

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The theory of the kinetics of metastable pit nucleation in terms of the Point Defect Model (PDM) has been applied the first time to describing the evolution of the nucleation rate of metastable pits on a variety of metallic substrates. The PDM successfully accounts for the experimental data that have been reported in the literature on stainless steel, carbon steel, iron, aluminum, and Alloy-22, and which are judged to be reliable and reproducible. Important fundamental parameters related to metastable pitting such as total number density of pitting nucleation sites, dissolution time of the cap over the pit, energy related to absorption of the aggressive ions into oxygen vacancies in the surface of the barrier layer, vacancy condensation rate, and the time at which the nucleation rate of metastable pits is maximum were obtained from the optimization of the PDM on the experimental data, as reported in the present paper. The values obtained for those parameters are in good agreement with values and observations reported elsewhere. The present work successfully demonstrates the capacity of the PDM in accounting for experimental observations of metastable pitting and that the PDM can be applied as an underlying theory for studying and understanding metastable pitting on metal surfaces. The passive state is not perfectly protective and passivity breakdown occurs for various reasons, giving rise to enhanced general corrosion rate or to localized corrosion. Localized passivity breakdown is especially of great concern, because it results in the nucleation and propagation of pits and the subsequent nucleation and growth of cracks provided that there is sufficient tensile stress in the system to initiate crack nucleation at the stress raiser represented by the pit. Metastable pitting, in which passivity breakdown occurs followed immediately by repassivation, is now well-accepted as being an integral part of the process of pitting corrosion on a metal or alloy, culminating in the accumulation of damage via the development of stable pits. It is also well-recognized that repassivation reflects the failure on the part of the pit nucleus to establish a spatial separation between the local cathode and the local anode with the former occurring on the external surfaces and the latter taking place in the nucleus, which is necessary for the buildup and maintenance of the aggressive conditions of high [Cl − ] and high [H + ] (low pH) that cause the pits to grow as stable pits, until they, too, die via delayed repassivation (due to the inability of the pit to maintain separation of the local cathode and the local anode, because of the limited availability of resources of the cathodic depolarizer on the external surfaces).Numerous authors have reported metastable pit nucleation rate data measured under more-or-less well-defined conditions. Williams et al.1-3 reported a good proportional correspondence for Type 304L SS between the nucleation frequency of metastable pits and the frequency of occurrence of propagating (stable) pits, that ...

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Section: Results and Analysis By Numerical Optimizationmentioning

confidence: 99%

“…Numerous models have been proposed for passivity breakdown, 2,7,11,19 and the Point Defect Model (PDM) is one of the only a few that has been demonstrated [20][21][22] to be capable of yielding relationships between the dependent (e.g. pitting potential and induction time) and the common independent (e.g.…”

mentioning

confidence: 99%

The Kinetics of Nucleation of Metastable Pits on Metal Surfaces: The Point Defect Model and Its Optimization on Data Obtained on Stainless Steel, Carbon Steel, Iron, Aluminum and Alloy-22

Lü

Engelhardt

Kursten

et al. 2016

J. Electrochem. Soc.

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“…The distribution in E b followed a near-normal distribution. The satisfactory correlation between the experimental and calculated distribution in E b confirms the validity of the point defect model (PDM) for describing the breakdown of the passive film on the grade of carbon steel tested [17].…”

Section: Pitting Corrosion Studiesmentioning

confidence: 67%

“…These current spikes are due to breakdown of the passive film followed immediately by repassivation (i.e. due to metastable pitting) [17].…”

Section: Pitting Corrosion Studiesmentioning

confidence: 99%

“…16 and was found to be insensitive to temperature. The critical areal concentration (ξ) of condensed cation vacancies at the metal/film (m/f) interface that leads to passivity breakdown, as predicted by the PDM, was calculated from the experimental dependence ( ) for vacancy condensation upon the metal lattice or upon the cation sublattice of the film, respectively [17]. The 'less than' operator precedes the experimentally determined value of ξ, because the passive current density, which is used in its calculation, is not due to the migration of cation vacancies alone, but is dominated by the migration of metal interstitials.…”

Section: Pitting Corrosion Studiesmentioning

confidence: 99%

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Corrosion issues of carbon steel radioactive waste packages exposed to cementitious materials with respect to the Belgian supercontainer concept

Kursten

Macdonald

Smart³

2017

Corrosion Engineering, Science and Technology

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The supercontainer is the reference concept for the post-conditioning of vitrified high-level radioactive waste and spent fuel in Belgium. It comprises a prefabricated concrete buffer that completely surrounds a carbon steel overpack. In this highly alkaline environment (pH ∼13.6) and under normal conditions (i.e. without the ingress of aggressive species), the carbon steel overpack will be protected by a passive oxide film, which is expected to result in very low uniform corrosion rates. Considering the long timescales applicable to waste disposal, determining accurate and reliable estimates of the uniform corrosion rate under anoxic conditions forms a very important part of the safety and feasibility strategy. On the other hand, the occurrence of localised forms of corrosion cannot be neglected and, therefore, it is also crucial to demonstrate that no other form of corrosion apart from uniform corrosion can take place. This paper gives an overview of the status of the research into the uniform corrosion, pitting corrosion and stress corrosion cracking behaviour of P355 QL2 grade carbon steel exposed to an artificial concrete pore water solution.ARTICLE HISTORY

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Effect of tungsten alloying on passivity breakdown of nickel

Al‐Sahli¹,

Ghanbari²,

Macdonald³

2018

Materials & Corrosion

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The addition of small amounts of tungsten (W) on the passivity breakdown of nickel (Ni) in borate buffer solutions as a function of chloride activity, pH, and voltage sweep rate has been evaluated and the data are interpreted in terms of the point defect model (PDM). The critical pitting potential of Ni–W alloys was found to become more positive (correspondingly a higher resistance to pitting) upon increasing the W content up to 3 at.% but decreases with further additions. The initial increase in the breakdown voltage with increasing [W] is attributed to changes in the diffusivity of the cation vacancy, the electric field strength, the annihilation rate of cation vacancies (Jm), changes in the standard Gibbs energy of adsorption of Cl− into surface oxygen vacancies, and in the standard Gibbs energy of generation of Schottky pairs, as predicted by the SVIM. At high [W] (4–5 at.%), it is postulated that all of the mobile cation vacancies are complexed with immobile WNi4⋅ [W(VI) cation substituted onto the Ni(II) vacancy of the cation sublattice of the barrier layer], so that further additions of W are predicted to have little positive effect in improving the pitting resistance of the alloy. Instead, W additions above 3% are postulated to increase the population density of breakdown sites on the surface via the formation of intermetallic precipitates, which has the effect of displacing the distribution in the breakdown voltage in the negative direction.

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Exploration of the effect of chloride ion concentration and temperature on pitting corrosion of carbon steel in saturated Ca(OH) 2 solution

Cited by 77 publications

References 53 publications

The Kinetics of Nucleation of Metastable Pits on Metal Surfaces: The Point Defect Model and Its Optimization on Data Obtained on Stainless Steel, Carbon Steel, Iron, Aluminum and Alloy-22

The Kinetics of Nucleation of Metastable Pits on Metal Surfaces: The Point Defect Model and Its Optimization on Data Obtained on Stainless Steel, Carbon Steel, Iron, Aluminum and Alloy-22

Corrosion issues of carbon steel radioactive waste packages exposed to cementitious materials with respect to the Belgian supercontainer concept

Effect of tungsten alloying on passivity breakdown of nickel

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