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.

This chapter focuses on resistance characteristics and methods of protecting different forms of high-temperature gaseous corrosion, namely high-temperature oxidation, sulfidation, carburization, hydrogen effects, and hot corrosion.

Stainless steels and nickel-base alloys are recognized for their resistance to general corrosion and other categories of corrosion. This chapter examines the effects of specific alloying elements, metallurgical structure, and mechanical conditioning on the corrosion resistance of these alloys. Some categories of corrosion covered are pitting, crevice, intergranular, stress-corrosion cracking, general, and high-temperature corrosion.

Elevated-temperature failures are the most complex type of failure because all of the modes of failures can occur at elevated temperatures (with the obvious exception of low-temperature brittle fracture). Elevated-temperature problems are real concerns in industrial applications. The principal types of elevated-temperature failure mechanisms discussed in this chapter are creep, stress rupture, overheating failure, elevated-temperature fatigue, thermal fatigue, metallurgical instabilities, and environmentally induced failure. The causes, features, and effects of these failures are discussed. The cooling techniques for preventing elevated-temperature failures are also covered.

This chapter describes the corrosion behavior of beryllium in gaseous atmospheres, including oxygen, nitrogen, carbon dioxide, and carbon monoxide. It also discusses the development of high-temperature corrosion-resistant beryllium alloys.

This chapter first covers some basic principles of electrochemical corrosion and then some of the various types of corrosion. Some of the more common types of corrosion discussed include uniform corrosion, galvanic corrosion, pitting, crevice corrosion, erosion-corrosion, cavitation, fretting corrosion, intergranular corrosion, exfoliation, dealloying corrosion, stress-corrosion cracking, and corrosion fatigue. The chapter discusses the processes involved in corrosion control by retarding either the anodic or cathodic reactions. The rate of corrosion is reduced by conditioning of the metal, by conditioning the environment, and by electrochemical control. Finally, the chapter deals with high-temperature oxidation that usually occurs in the absence of moisture.

This chapter outlines the topics covered in the book and explains why and to whom the book was written. The book is intended for engineers, metallurgists, and failure analysts who work with materials and components that operate in high-temperature corrosive environments. It covers eight basic modes of high-temperature corrosion as well as the effect of external and residual stresses. It also provides an extensive amount of engineering data associated primarily with commercial alloys.

This chapter explains how materials selection becomes much more difficult when designing for high-temperature corrosion environments. It also discusses the use of cladding and weld overlays to compensate for material deficiencies and prolong service life.

This chapter discusses the conditions under which carburization and metal dusting occur. It describes the chemical reactions and thermodynamic relationships that drive carburization and metal dusting attack and the factors that determine the amount of damage that metals and alloys are likely to sustain. The chapter also explains how carburization affects creep strength and fracture toughness, and how surface conditions and finish and the presence of sulfur affect metal dusting behaviors.

Alloys containing elements that form volatile or low-melting-point halides are susceptible to high-temperature corrosion attack. This chapter explains how to determine whether such phases are likely to form, and the rate at which they occur, based on thermodynamic data and phase stability diagrams. It provides an extensive amount of high-temperature corrosion data for metals and alloys in gaseous environments containing chlorine and hydrogen chloride; fluorine and hydrogen fluoride; bromine and hydrogen bromide; and iodine and hydrogen iodide.

This chapter examines the hot corrosion resistance of various nickel- and cobalt-base alloys in gas turbines susceptible to high-temperature (Type I) and low-temperature (Type II) hot corrosion. Type I hot corrosion is typically characterized by a thick, porous layer of oxides with the underlying alloy matrix depleted in chromium, followed (below) by internal chromium-rich sulfides. Type II hot corrosion is characterized by pitting with little or no internal attack underneath. As the chapter explains, chromium additions make alloys more resistant to all types of hot corrosion attacks.

Fireside corrosion can be a serious problem in oil-fired boilers and in refinery furnaces fired with low-grade fuels. This chapter provides an overview of fireside or oil-ash corrosion and the problems it can cause in utility power boilers and petrochemical refinery furnaces. It explains how oil-ash corrosion affects waterwalls, superheaters, and reheaters as well as metal tube supports and hangers.

This chapter discusses two damage mechanisms in which stress plays a major role. In the one case, stress causes cracks in the oxide scale on metals, leading to preferential corrosion attack. An example from industry of this type of failure is the circumferential cracking that occurs on the waterwall tubes of supercritical coal-fired boilers fired under low NOx combustion conditions, conducive to the production of sulfidizing environments. In the other case, stress contributes to brittle fracture in the form of intergranular cracking. The phenomenon, which is known by various names, typically occurs at the lower end of the intermediate temperature range and has been observed in ferritic steels, stainless steels, Fe-Ni-Cr alloys, and nickel-base alloys, as described in the chapter.

Containment materials used in power generating applications are subject to molten salt corrosion. This chapter reviews the data relevant to corrosion problems in molten salt environments. It describes the corrosion behavior of steel, aluminum, nickel, and titanium alloys in molten chlorides, molten nitrates, molten fluorides, molten carbonates, and molten sodium hydroxide.

Carbon and low-alloy steels in high-temperature service are vulnerable to the effects of hydrogen attack, which include severe loss in tensile and rupture strengths as well as ductility. As the chapter explains, when steel is in contact with hydrogen molecules at elevated temperatures, hydrogen atoms can be absorbed at the surface and then diffuse into the metal. Hydrogen atoms in the metal then react with iron carbide forming methane gas which can accumulate at grain boundaries and other interfaces. The chapter describes two applications, one in coal-fired boilers, the other in petroleum refining, where hydrogen attack was observed. It documents the extent of the damage in each case and identifies the source of the hydrogen.

This appendix is a compilation of trademarked materials used in high-temperature corrosion applications and the associated producers or suppliers.

Superalloys tend to operate in environments where they are subjected to high-temperature corrosion, oxidation, and the erosive effects of hot gases. This chapter discusses the nature of these attacks and the effectiveness of various protection methods. It describes the primary forms of oxidation, the development of protective oxides, and the conditions associated with mixed gas corrosion and hot corrosion attack. It discusses oxidation and corrosion testing, the equipment used, and various ways to present the associated data. It describes the effect of gaseous oxidation on different alloys, discusses the formation of oxide scale in the presence of mixed gases, and explains how alloy composition contributes to oxide growth. The chapter discusses the underlying chemistry of hot corrosion, how to identify its effects, and how it progresses under various conditions. It also discusses protective coatings, including aluminide diffusion, overlay, and thermal barrier types, and how they perform in different environments based on their ability to tolerate strain.