Probability distribution of pitting corrosion depth and rate in underground pipelines: A Monte Carlo study

The probability distributions of external-corrosion pit depth and pit growth rate were investigated in underground pipelines using Monte Carlo simulations. The study combines a predictive pit growth model developed by the authors with the observed distributions of the model variables in a range of soils. Depending on the pipeline age, any of the three maximal extreme value distributions, i.e. Weibull, Fréchet or Gumbel, can arise as the best fit to the pitting depth and rate data. The Fréchet distribution best fits the corrosion data for long exposure periods. This can be explained by considering the long-term stabilization of the diffusion-controlled pit growth. The findings of the study provide reliability analysts with accurate information regarding the stochastic characteristics of the pitting damage in underground pipelines.     

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.     

Stochastic approach to pitting-corrosion-extreme modelling in low-carbon steel

A stochastic model previously developed by the authors using Markov chains has been improved in the light of new experimental evidence. The new model has been successfully applied to reproduce the time evolution of extreme pitting corrosion depths in low-carbon steel. The model is shown to provide a better physical understanding of the pitting process.     

Spatial statistics of pitting corrosion patterning: Quadrat counts and the non-homogeneous Poisson process

This paper presents a stochastic analysis of spatial point patterns as effect of localized pitting corrosion. The Quadrat Counts method is studied with two empirical pit patterns. The results are dependent on the quadrat size and bias is introduced when empty quadrats are accounted for the analysis. The spatially inhomogeneous Poisson process is used to improve the performance of the Quadrat Counts method. The latter combines Quadrat Counts with distance-based statistics in the analysis of pit patterns. The Inter-Event and the Nearest-Neighbour statistics are here implemented in order to compare their results. Further, the treatment of patterns in irregular domains is discussed.     

New insight into the pit-to-crack transition from finite element analysis of the stress and strain distribution around a corrosion pit

A finite element (FE) analysis has been undertaken to evaluate the stress and strain distribution associated with a single corrosion pit in a cylindrical steel specimen stressed remotely in tension. A key observation was the localisation of plastic strain to the pit walls (just below the surface of the specimen). Simulation of a growing pit in a static stress field indicated corresponding plastic strain rates that were commensurate with values associated with stress corrosion cracking. This observation introduces a wholly new concept in understanding of the evolution of stress corrosion cracks from pits and correlates with recent X-ray tomography measurements.     

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.     

Employing electrochemical frequency modulation for pitting corrosion

By using the electrochemical frequency modulation (EFM) technique, the non-linear behavior of a corroding system is measured. This non-linear behavior is likely to be different for a system undergoing uniform or pitting corrosion. The implementation of the EFM technique to detect pitting corrosion has been investigated by observing the fluctuations in the so-called causality factors. These causality factors, resulting from an EFM test and in the ideal case having values of 2 and 3, respectively, are normally used for quality and data validation purposes. While investigating pitting corrosion, they show different behavior leading to the CPT (critical pitting temperature) detection.     

A generic statistical methodology to predict the maximum pit depth of a localized corrosion process

This paper outlines a new methodology to predict accurately the maximum pit depth related to a localized corrosion process. It combines two statistical methods: the Generalized Lambda Distribution (GLD), to determine a model of distribution fitting with the experimental frequency distribution of depths, and the Computer Based Bootstrap Method (CBBM), to generate simulated distributions equivalent to the experimental one. In comparison with conventionally established statistical methods that are restricted to the use of inferred distributions constrained by specific mathematical assumptions, the major advantage of the methodology presented in this paper is that both the GLD and the CBBM enable a statistical treatment of the experimental data without making any preconceived choice neither on the unknown theoretical parent underlying distribution of pit depth which characterizes the global corrosion phenomenon nor on the unknown associated theoretical extreme value distribution which characterizes the deepest pits.Considering an experimental distribution of depths of pits produced on an aluminium sample, estimations of maximum pit depth using a GLD model are compared to similar estimations based on usual Gumbel and Generalized Extreme Value (GEV) methods proposed in the corrosion engineering literature. The GLD approach is shown having smaller bias and dispersion in the estimation of the maximum pit depth than the Gumbel approach both for its realization and mean. This leads to comparing the GLD approach to the GEV one. The former is shown to be relevant and its advantages are discussed compared to previous methods.     

Multifractal modelling of electrochemical noise in corrosion of carbon steel

Electrochemical noise analysis of corroding surfaces provides useful information regarding the temporal changes in material degradation, corrosion mechanisms and condition monitoring. In this study, we analyzed the electrochemical potential and current noise originating from the corrosion of carbon steel (ASTM A106) in distilled water using multifractal analysis. The empirical Legendre spectrum and large deviation singularity spectrum are determined for the electrochemical noise at different stages of corrosion. A wavelet-based multifractal model is introduced to describe the multiscaling behaviour.     

Numerical simulation of a single corrosion pit in CO2 and acetic acid environments

The present paper bears on a numerical model of steady-state behaviour of a single corrosion pit in CO₂-containing media in the presence of acetic acid. The kinetics of electrochemical reactions occurring on the electrode surface is described by Tafel equations fitted to experimental data obtained on API 5L X65 pipeline steel. Simulation results provide an interesting insight into both the chemistry and electrochemistry inside the active pit. Particular attention is paid to the effect of HAc on the coupling behaviour between the attack base and the outer surrounding surface and to the comparison with experimental data obtained in similar conditions.     

The initial stage of pitting corrosion on coated steels investigated by photon rupture in chloride containing solutions

A photon rupture method, film removal by a focused pulse of pulsed Nd-YAG laser beam irradiation, has been developed to enable oxide film stripping at extremely high rates without contamination from the film removal tools. In the present study, Zn-55mass%Al alloy and Al-9mass%Si alloy-coated steel specimens covered with protective nitrocellulose film were irradiated with a focused pulse of a pulsed Nd-YAG laser beam at a constant potential in 0.5 kmol m⁻³ H₃BO₃-0.05 kmol m⁻³ Na₂B₄O₇ (pH = 7.4) with 0.01 kmol m⁻³ of chloride ions to investigate the initial stage of localized corrosion. At low potentials, oxide films on both coated alloys were reformed after the nitrocellulose films were removed by this method. The oxide film formation kinetics follows an inverse logarithmic law, in agreement with Cabrera-Mott theory. However, at high potentials, localized corrosion producing corrosion products occurs at the area where nitrocellulose film was removed. Nevertheless, when the applied potential is less noble, the dissolution current of the Zn-55mass%Al-coated steel samples is higher than that of Al-9mass%Si-coated samples.     

Stable pitting corrosion of stainless steel as diffusion-controlled dissolution process with a sharp moving electrode boundary

This paper is devoted to explanation and prediction of pit propagation or stable pit growth, governed by ion transport properties in electrolytic solutions. Therefore, we vigorously derive the (3D) mass conservation law for a body hosting a sharp metal/solution interface separating the solid electrode from liquid electrolyte. The model for stable pitting corrosion is completed by Fick’s law of diffusion, governing the behavior of the dissolved metal ions. There are only three model input values, which are directly accessible from experiments, namely the ion concentration in the solid metal, as well as the diffusion coefficient and the saturation concentration of the dissolved metal ions in the electrolyte. The partial differential equations describing stable pitting corrosion as diffusion-controlled dissolution process are solved for boundary conditions related to 1D pencil electrode tests as well as to 2D foil electrode tests. The mathematical solution functions (model predictions) are related to pit growth in terms of depth and width, and to electric current evolution. Such model predictions reasonably agree with corresponding experiments, which shows the relevance of the proposed approach. In the case of pits with lacy covers, the boundary conditions for the ionic flux probably depend on complex depassivation-repassivation phenomena. However, once the extent of perforation of the lacy cover is known, the entire pit propagation characteristics, in particular the pit shape, can be predicted by the proposed model, relating to a classical Stefan problem.     

Effect of microcrystallization on pitting corrosion of pure aluminium

A microcrystalline aluminium film with grain size of about 400 nm was prepared by magnetron sputtering technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of potentiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the corrosion potential of the sample shifted towards more positive direction, while its corrosion current density decreased compared with that of pure coarse-grain Al. The EN analysis based on stochastic model demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to the enhancement of pitting resistance for the microcrystallized aluminium.     

Quantum chemical study of some cyclic nitrogen compounds as corrosion inhibitors of steel in NaCl media

Corrosion inhibition efficiencies of 3-amino-1,2,4-triazole (3-ATA), 2-amino-1,3,4-thiadiazole (2-ATDA), 5-(p-tolyl)-1,3,4-triazole (TTA), 3-amino-5-methylmercapto-1,2,4-triazole (3-AMTA) and 2-aminobenzimidazole (2-ABA) as corrosion inhibitors on steel in sodium chloride media were investigated by using semiempirical PM3 and density functional theory (DFT) methods. Quantum chemical parameters such as highest occupied molecular orbital energy (E_HOMO), lowest unoccupied molecular orbital energy (E_LUMO), energy gap (ΔE) and dipole moment (μ) have been calculated for these compounds by using semiempirical PM3 and 6-31G(d), 6-311G(d,p) DFT methods. It was found that theoretical data support the experimental results.     

Pitting corrosion in low carbon steel influenced by remanent magnetization

A new type of experiment is performed using a closed magnetic circuit configuration in order to study the influence of the magnetic field on pitting corrosion in low carbon pipeline steel. The statistical assessment of the pitting corrosion data shows that the magnetic field in the material under test reduces the extreme pit depths and also the average depth of the pit population. It is proposed that reduction in pit depth under the influence of remanent magnetization can be explained based on the behavior of the paramagnetic corrosion products under the influence of the magnetic field gradient produced inside pits.     

Chloride threshold level for corrosion of steel in concrete

The steel rebar inside reinforce concrete structures is susceptible to corrosion when permeation of chloride from deicing salts or seawater results in the chloride content at the surface of the steel exceeding a chloride threshold level (CTL). The CTL is an important influence on the service life of concrete structures exposed to chloride environments. The present study discusses the state of art on the CTL for steel corrosion in concrete, concerning its measurement, representation, influencing factors and methods to enhance the CTL. As the CTL values reported in the majority of previous studies were varied with experimental conditions, corrosion initiation assessment method, the way in which the CTL was represented, direct comparison between the results from different sets and evaluation was subjected to the difficulty. As a result, total chloride by weight of cement or the ratio of [Cl⁻]:[H⁺] is the best presentation of CTL in that these include the aggressiveness of chlorides (i.e. free and bound chlorides) and inhibitive nature of cement matrix. The key factor on CTL was found to be a physical condition of the steel-concrete interface, in terms of entrapped air void content, which is more dominant in CTL rather than chloride binding, buffering capacity of cement matrix or binders. The measures to raise the CTL values using corrosion inhibitor, coating of steel, and electrochemical treatment are also studied.     

Effect of corrosion severity on fatigue evolution in Al-Zn-Mg-Cu

The effect of existing-localized corrosion on fatigue cracking of 7075-T6511 was established using crack surface marker-band analysis and a fracture mechanics model. The substantial reduction of fatigue life due to EXCO solution L-S surface pre-corrosion is nearly independent of exposure time after initial-sharp degradation, scaling with the evolution of pit-cluster size and initial stress intensity range with exposure time. Independent of exposure time, formation of a resolvable fatigue crack (∼10 μm) accounts for a similar-low (∼5%) fraction of total fatigue life at low stress range (σ_max = 150 MPa, R = 0.1). Crack formation occurs at microscopic protrusions into the corroded volume. A corrosion-modified-equivalent initial flaw size (CM-EIFS); predicted with the AFGROW tool using measured initial aspect ratio, initiation cycles, and total fatigue life inputs; accurately represents the corrosion damage effect on fatigue for a range of exposures. The similar deleterious effect of several corroding environments for various-exposed surfaces is described by a lower-bound CM-EIFS with a 300 μm depth and 1200 μm surface length suggesting fatigue is governed by a microscopic pit-based topography. Either an approximate lower-bound, or specific CM-EIFS calibrated by limited measurements of fatigue life for service-environment exposed specimens, can be used to assess the impact of corrosion in a damage tolerant framework. Complexities (e.g., local H embrittlement, 3D pit geometry, topography dependent initiation, and microstructure sensitive small-crack growth) do not compromise the CM-EIFS estimation, but must be better understood for refined modeling.     

Influence of ultrasound on pitting corrosion and crevice corrosion of SUS304 stainless steel in chloride sodium aqueous solution

The change of polarization curves and surface morphologies of SUS304 stainless steel was investigated in 3.5 mass% NaCl solution with or without the application of ultrasound (US). As the result, both the pitting corrosion and the crevice corrosion were largely suppressed by the application of US. The reason is attributed to the decrease in the concentration of hydrogen and chloride ions in pits or in the crevice by removing the corrosion product and stirring the liquid there.