B. Rammer, M.C. Galetz
Materials and Corrosion 68 (2017), 186-196, DOI: 10.1002/maco.201608841
Operating atmospheres of many industrial high temperature processes contain a certain amount of halogens, in most cases chlorine. Halogens have the tendency of forming volatile metal chlorides of the general formula MxCly, which are well known to play a critical role in high temperature corrosion processes, when present at a significant amount. Thermodynamic calculations give a valuable hint, whether a reaction product can occur and how volatile such products can potentially be, when the partial pressures are calculated. However, such calculations reflect thermodynamically stable conditions, while in open systems the local kinetics control the process of surface reactions. For each specific condition, the reaction rates and thus the corrosion rates have to be determined. In previous work, we have shown that corrosion kinetics which lead to the formation of volatile products follows different steps. In this work, a mathematical model is developed in which the different steps, which are required for the formation of metal chlorides and their removal from the surface are described. It is assumed that the slowest of such formation or transport steps determines the kinetics of high temperature corrosion. The application of this model on the literature data shows that by this model it becomes possible to identify the slowest and therefore rate determining step.