High-temperature corrosion thermodynamics oxidation kinetics

Chapter 10 deals with high temperature corrosion, in which the thermodynamics and kinetics of metal oxidation are included. The Pilling Bedworth Ratio and Wagner s parabolic rate constant theories are defined as related to formation of metal oxide scales, which are classified as protective or nonprotec-tive. 

The overall simulation of high-temperature corrosion processes under near-service conditions requires both a thermodynamic model to predict phase stabilities for given conditions and a mathematical description of the process kinetics, i.e. solid state diffusion. Such a simulation has been developed by integrating the thermodynamic program library, ChemApp, into a numerical finite-difference diffusion calculation, InCorr, to treat internal oxidation and nitridation of Ni-base alloys [10]. This simulation was intended to serve as a basis for an advanced computer model for internal oxidation and sulfidation of low-alloy boiler steels. 

It is important to realize that corrosion rates may be controlled by any of several thermodynamic or kinetic properties of the alloy-scale-environment system and not just by surface or interface reactions. The three stages of high temperature oxidation of a metal, shown schematically in Fig. 1, serve as an example (7). The first or transient stage includes initial gas adsorption, two-dimensional oxide nucleation, initial three-dimensional oxide formation and finally, formation of the dominant oxide that will control the oxidation rate in Stage II. Various portions of Stage I have been widely studied using surface analytical techniques, but its duration can be very short and it is usually assumed (not always correctly) that Stage I has little impact on ultimate corrosion properties of the material. 

The heart of corrosion science has been identified as electrochemical science coupled with the thermodynamic and kinetic values. Other limbs are oxidation and high-temperature oxidation of metals, protective coatings, passivity, inhibitors, microbial-induced corrosion, corrosion fatigue, hydrogen embrittlement and corrosion-resistant alloys. Having identified the limbs of corrosion science, it is instructive to examine how the various aspects came into existence over a period of time. 

The third alternative presented is the development of the InCorr tool for internal and inward corrosion, based on finite element calculations. This method is based on thermodynamic stability calculations with solid state diffusion algorithms. The model examples describe high-temperature oxidation kinetics for a 2.25Cr steel and the results are in good agreement with the corresponding experimental studies and analyses. 

---