Modeling Silver Corrosion Mechanisms in Marine Atmospheric Environments

Abstract

Measures that can assess the severity of the local environment are an important tool for combating atmospheric corrosion. One approach for determining the environmental severity employs electrochemical analysis alongside surface characterization on silver coupons exposed to the environment for varying durations. However, despite the long use of silver as an environmental severity monitor, the underlying reaction mechanisms that give rise to the observed corrosion products are not well understood. In addition, the measured ratios of silver corrosion products appear to be unique to the location where the silver coupons were exposed.The goal of this work is to develop models of silver oxidation reactions that can explore pathways for the formation of silver corrosion products. We use density functional theory (DFT) calculations in nudged elastic band (NEB) approximations to determine electrochemical and chemical reaction along with surface diffusion energy barriers. An example reaction is shown in Figure 1a and b, in which an O2 molecule is adsorbed on an ‘on-top’ site on a relaxed Ag (100) crystal structure with periodic boundary conditions in the x and y-planes. The O2 molecule then dissociates into individual O atoms. The reaction pathway is approximated using the NEB approach to determine the dissociation energy barrier in Figure 1c. These reaction energy barriers are incorporated into a kinetic Monte Carlo (KMC) model of silver reactions to estimate the corrosion products present in marine atmospheric environments for comparison with experimental data. Figure 1