Effects of porosity in a model of corrosion and passive layer growth

TL;DR

This paper introduces a stochastic lattice model to study how pore formation affects corrosion and passive layer growth, revealing that porosity and pore size significantly influence growth rate and surface roughness.

Contribution

The model incorporates pore formation and diffusion effects, providing new insights into passive layer growth and defect influence on corrosion processes.

Findings

Small porosity slows passive layer growth due to ion confinement.

Large pores increase corrosion front roughness and reaction frequency.

Porosity and pore size critically affect corrosion dynamics.

Abstract

We introduce a stochastic lattice model to investigate the effects of pore formation in a passive layer grown with products of metal corrosion. It considers that an anionic species diffuses across that layer and reacts at the corrosion front (metal-oxide interface), producing a random distribution of compact regions and large pores, respectively represented by O (oxide) and P (pore) sites. O sites are assumed to have very small pores, so that the fraction $\Phi$ of P sites is an estimate of the porosity, and the ratio between anion diffusion coefficients in those regions is $D_{\text r}<1$. Simulation results without the large pores ($\Phi =0$) are similar to those of a formerly studied model of corrosion and passivation and are explained by a scaling approach. If $\Phi >0$ and $D_{\text r}\ll 1$, significant changes are observed in passive layer growth and corrosion front roughness. For small $\Phi$, a slowdown of the growth rate is observed, which is interpreted as a consequence of the confinement of anions in isolated pores for long times. However, the presence of large pores near the corrosion front increases the frequency of reactions at those regions, which leads to an increase in the roughness of that front. This model may be a first step to represent defects in a passive layer which favor pitting corrosion.