Fossil fuels produce many byproducts that, if not fully combusted, put boiler tubes at risk. Fuel ash, chemical residues, and process heat pose the greatest threat and are the primary contributors to fireside corrosion. This chapter covers various types of fireside corrosion such as waterwall, fuel ash, and hot corrosion, acid dew-point or cold-end corrosion, and polythionic acid corrosion. It also addresses stress corrosion cracking and includes relevant case studies.

Corrosive environments can be broadly classified as atmospheric, underground/soil, water, acidic, alkaline, and combinations of these. Complicating matters is the fact that there are important variables, for example, pH, temperature, and the presence of biological organisms, that can significantly alter the response of the material in a given environment. This chapter provides a detailed account of all these types of corrosion affecting various industries, pointing out the connection between the characteristics of the corrosive environment that control corrosion behavior, the corrosion characteristics of various metals and materials systems, and the subsequent corrosion response.