The Effects of Water Vapor and Hydrogen on the High-Temperature Oxidation of Alloys

Essentially all alloys and coatings that are resistant to corrosion at high temperature require the formation of a protective (slowly-growing and adherent) oxide layer by a process known as selective oxidation. The fundamental understanding of this process has been developed over the years for exposure in pure oxygen or air. However, the atmospheres in most applications contain significant amounts of water vapor which can greatly modify the behavior of protective oxides. The development of oxy-fuel combustion systems in which fossil fuels are burned in a mixture of recirculated flue gas and oxygen, rather than in air, has caused renewed interest in the effects of water vapor and steam on alloy oxidation. The focus of this paper is on the ways the presence of water vapor can directly alter the selective oxidation process. The paper begins with a brief review of the fundamentals of selective oxidation followed by a description of recent experimental results regarding the effect of water vapor on the oxidation of a variety of chromia-forming alloys (Fe- and Ni-base) in the temperature range 600 to 700 °C. The atmospheres include air, air-H2O, Ar-H2O and Ar-H2O-O2. Then the behavior of alumina-forming alloys in H2O-containing atmospheres is briefly described. As hydrogen is produced during oxidation of alloys in H2O, it can be released back into the gas phase or injected into the metal (where it can diffuse through to the other side). Experiments in which hydrogen concentrations have been measured on both sides of thin specimens during oxidation by H2O on only one side are described. Finally, it is attempted to catalogue the various experimental observations under a few general principles.