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

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.Comment: 8 pages, 6 figure

Roughness exponents and grain shapes

In surfaces with grainy features, the local roughness $w$ shows a crossover at a characteristic length $r_c$, with roughness exponent changing from $\alpha_1\approx 1$ to a smaller $\alpha_2$. The grain shape, the choice of $w$ or height-height correlation function (HHCF) $C$, and the procedure to calculate root mean-square averages are shown to have remarkable effects on $\alpha_1$. With grains of pyramidal shape, $\alpha_1$ can be as low as 0.71, which is much lower than the previous prediction 0.85 for rounded grains. The same crossover is observed in the HHCF, but with initial exponent $\chi_1\approx 0.5$ for flat grains, while for some conical grains it may increase to $\chi_1\approx 0.7$. The universality class of the growth process determines the exponents $\alpha_2=\chi_2$ after the crossover, but has no effect on the initial exponents $\alpha_1$ and $\chi_1$, supporting the geometric interpretation of their values. For all grain shapes and different definitions of surface roughness or HHCF, we still observe that the crossover length $r_c$ is an accurate estimate of the grain size. The exponents obtained in several recent experimental works on different materials are explained by those models, with some surface images qualitatively similar to our model films.Comment: 7 pages, 6 figures and 2 table