Predictive Modeling of Corrosion

Macdonald, Digby D.; Engelhardt, George R.

doi:10.1016/b978-044452787-5.00086-x

Cited by 41 publications

(82 citation statements)

References 81 publications

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“…The PDM postulates that if the cation vacancies arriving at the metal-barrier layer interface cannot be annihilated at a sufficiently high rate, the excess vacancies will condense at metal/barrier layer interface, which results in local separation of the barrier layer from the metal substrate to form a blister and, eventually, in the rupture of the remaining cap of the blister, because of the growth stress in the film and in the near-surface substrate [24,25]. Mathematically, this condition for passivity breakdown can be expressed as…”

Section: Resultsmentioning

confidence: 99%

“…Ca(OH)2 + X,M NaCl (pH 12.5 ± 0.1 at 25 • C) with different chloride concentrations. experimental data, we define the cumulative probability in breakdown potential as follows [24,25,57]: where…”

Section: Resultsmentioning

confidence: 99%

“…The goals of the present work are to: (1) study the localized corrosion behavior of carbon steel in saturated Ca(OH) 2 as a function of temperature, chloride ion concentration, and potential scan rate; (2) statistically analyze the relationship between the passivity breakdown potential versus chloride ion concentration and temperature in terms of the point defect model [9,[22][23][24][25][26][27], in order to extract the model parameters, and (3) Demonstrate that the PDM incorporating a normal distribution of the potential breakdown sites on the surface with respect to the diffusivity of cation vacancies in the barrier layer, adequately accounts for the experimentally observed distribution in the critical breakdown voltage.…”

Section: Introductionmentioning

confidence: 99%

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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

et al. 2015

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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

et al. 2015

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“…It is noted that chloride concentration (or activity) is an important environmental variable that has a great effect on the induction time and its distribution, although it does not appear in equations (14) and (16) directly. However, increasing chloride concentration decreases the mean breakdown potential V c and hence, increases the breakdown overvoltage (DV~V {V c ) for a given value of the applied voltage V and also tends to decrease the standard deviation s D in the cation vacancy diffusivity D. Both increasing DV and decreasing s D are conducive to decreasing the induction time and narrowing the distribution in the induction time.…”

Section: Passivity Breakdown and Accumulation Of Pitting Damagementioning

confidence: 97%

“…14 The PDM provides an analytical relationship between the apparent breakdown potential V c (u) and u in the form of equation (4), 31 which can be used to determine the ratio…”

Section: Passivity Breakdown and Accumulation Of Pitting Damagementioning

confidence: 99%

Passivity: enabler of our metals based civilisation

Macdonald

2014

Corrosion Engineering, Science and Technology

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The origin of passivity, as viewed from the Point Defect Model, is presented in terms of the phase space analysis of the rate law for the growth of passive films. It is shown that passivity is due to the formation of a metastable oxide and hence, the occurrence of passivity is a kinetic phenomenon, in which the rate of film growth of the oxide at the metal/barrier layer interface into the metal at zero barrier layer thickness must exceed the rate of barrier layer dissolution at the barrier layer/solution (bl/s) interface, in order for the barrier layer to exist. If this relationship does not hold, the barrier layer disappears and the surface becomes depassivated. Depassivation is illustrated with respect to transpassive dissolution, acid depassivation, pitting corrosion, flow assisted corrosion, impingement attack, resistive depassivation and other phenomena. The theory also leads to the development of Kinetic Stability Diagrams (KSDs), in which the potential for depassivation is plotted against pH to define regions of depassivation and passivation, so that regions in potential versus pH space can be defined within which passive films may exist as protective, metastable entities. The author offers these diagrams as kinetically inspired alternatives to the classical Pourbaix diagrams. One form of depassivation that occurs at highly localised regions on a metal surface is pitting corrosion. The theory for pitting is now highly developed and certain aspects of the subject are reviewed here. It is argued that the theory of pitting is sufficiently well established that the deterministic prediction of pitting damage is practical, in many systems. The theory is illustrated here with respect to the pitting of Type 403 stainless steel (SS), which is used extensively for the manufacture of low pressure steam turbines in steam cycle systems for the generation of electrical power.

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Pitting of carbon steel in the synthetic concrete pore solution

Macdonald

Qiu

Sharifi‐Asl

et al. 2020

Materials & Corrosion

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Pitting corrosion is a possible mode of failure of the carbon steel overpack of the Belgian supercontainer concept for the isolation of high‐level nuclear waste (HLNW). However, no firm experimental data are currently available to estimate the probability of failure over the extended storage time (100,000 years). Extensive work shows that passivity breakdown results from the condensation of cation vacancies (CVs) at the metal/barrier layer (m/bl) interface, in response to the absorption of Cl− into oxygen vacancies at the surface of the barrier oxide layer. The CVs migrate across the bl to the m/bl interface where they condense, leading to the separation of the bl from the metal. The resulting blister prevents the growth of bl into the metal and dissolution results in blister rupture, marking a passivity breakdown event. Stabilization via differential aeration produces a potentially damaging, stable pit. We review our work on passivity breakdown and the nucleation of pits on P355 QL2 carbon steel in high‐pH aqueous media typical of concrete pore solution, with emphasis on the mechanistic aspects. We conclude that failure of the carbon steel overpack containing the HLNW over a storage horizon of 100,000 years is improbable.

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Predictive Modeling of Corrosion

Cited by 41 publications

References 81 publications

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

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

Passivity: enabler of our metals based civilisation

Pitting of carbon steel in the synthetic concrete pore solution

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