Scaling theory in a model of corrosion and passivation

TL;DR

This paper develops a scaling theory for corrosion and passivation of metals, linking microscopic reaction rates and diffusion processes to the incubation time and size of corrosion pits, supported by numerical simulations.

Contribution

It introduces a novel scaling theory connecting reaction-diffusion dynamics to corrosion incubation, validated by 2D simulations and applicable to 3D systems.

Findings

Average radius of corrosion region depends on reaction rates and diffusion coefficients.

Incubation time linearly relates to neutral dissolution rate.

Numerical simulations confirm the theoretical predictions.

Abstract

We study a model for corrosion and passivation of a metallic surface after small damage of its protective layer. The crossover from an initial regime of slow corrosion rate (pit nucleation) to a regime of rapid corrosion (propagation of the pit) takes place at the incubation time. The model is defined in a lattice whose sites represent the possible states of the metal (bulk, reactive and passive) and the solution (neutral, acidic or basic). Probabilistic rules describe passivation of the metal surface, dissolution of the passive layer, which is enhanced in acidic media, and spatially separated electrochemical reactions, which may create pH inhomogeneities in the solution. From a suitable matching of characteristic times of creation and annihilation of pH inhomogeneities in the solution, a scaling theory gives the average radius of the dissolved region at the incubation time as a function of the model parameters. That radius decreases with the rate of spatially separated reactions and the rate of dissolution in acidic media, and increases with the diffusion coefficient of H+ and OH- ions in solution. The average incubation time is written as the sum of a series of characteristic times for the slow dissolution in neutral media. It linearly increases with the rate of dissolution in neutral media, under the reasonable assumption that this is the slowest rate of the process. The results are confirmed by numerical simulation in two-dimensional lattices, but extension to three dimensions is discussed.