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 provides an outline of the failure modes and mechanisms associated with most boiler tube failures in coal-fired power plants. Primary categories include stress rupture failures, water-side corrosion, fire-side corrosion, fire-side erosion, fatigue, operation failures, and insufficient quality control.

Irradiation-assisted stress-corrosion cracking (IASCC) has been a topic of engineering interest since it was first reported in the 1960s, having been observed in stainless steel cladding on light water reactor fuel elements. This chapter summarizes the results of decades of investigation, showing that IASCC can essentially be defined as the intergranular cracking of austenitic alloys in high-temperature water, where both the material and its environment have been altered by radiation. Of the many interactions that can occur when metals and water are exposed to radiation, the international consensus is that the three with the greatest impact on crack growth rates are the formation of material defects, radiation-induced segregation, and chemical reactions that increase the corrosion potential of water. The chapter discusses each of these in great detail, and includes information on predictive modeling as well.

This chapter provides an introduction to various forms of corrosion, namely uniform corrosion, localized corrosion, mechanically assisted degradation, environmentally induced cracking, microbiologically influenced corrosion, and metallurgically influenced corrosion.

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 appendix is a collection of tables listing the chemical compositions of wrought ferritic steels; wrought stainless steels; cast corrosion- and heat-resistant alloys; wrought iron-, nickel-, and cobalt-base alloys; cast nickel- and cobalt-base alloys; oxide-dispersion-strengthened alloys; and iron-, nickel- and cobalt-base filler metals.

Many metallic components, such as retorts in heat treat furnaces, furnace heater tubes and coils in chemical and petrochemical plants, waterwalls and reheater tubes in boilers, and combustors and transition ducts in gas turbines, are subject to oxidation. This chapter explains how oxidation affects a wide range of engineering alloys from carbon and Cr-Mo steels to superalloys. It discusses the kinetics and thermodynamics involved in the formation of oxides and the effect of surface and bulk chemistry. It provides oxidation data for numerous alloys and intermetallics in terms of weight gain, metal loss, depth of attack, and oxidation rate. It also discusses the effect of metallurgical and environmental factors such as oxygen concentration, high-velocity combustion gas streams, chromium depletion and breakaway, component thickness, and water vapor.

Oxidation usually dominates high-temperature corrosion reactions, but under certain conditions, some alloys may be affected by nitridation as well. This chapter explains why nitridation occurs and how it attacks various metals, in some cases, penetrating deeper than oxidation. It provides images and data describing the nitridation process and its effects on metals and alloys in high-temperature air as well as NH3-H2O, NH3 and H2-N2-NH3, and N2 environments. It also includes test data showing that nitridation is more severe in a nitrogen atmosphere than an ammonia environment at 1090 °C (2000 °F).

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.

Sulfur is one of the most common corrosive contaminants in high-temperature industrial environments and its presence can cause a number of problems, including sulfidation. This chapter describes the sulfidation behavior of a wide range of alloys as observed in three types of industrial environments. One environment consists of sulfur vapor, hydrocarbon streams, H2S, and H2-H2S gas; sulfides are the only corrosion products that form under these conditions. Another environment consists of H2, CO, CO2, H2S, and other gases, causing the formation of oxides as well as sulfides in most alloys. The third environment, for which less data exists, contains either SO2 or O2-SO2 mixtures.

This chapter discusses the erosion and erosion-corrosion behaviors of metals and alloys. It includes data primarily related to particle-laden gas streams impacting on the metal surface. It also covers properties and applications and provides guidelines for materials selection.

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.

This chapter discusses material-related problems associated with coal-fired burners. It explains how high temperatures affect heat-absorbing surfaces in furnace combustion areas and in the convection pass of superheaters and reheaters. It describes how low-NOx combustion technology, intended to reduce NOx emissions, accelerates tube wall wastage. It also covers circumferential cracking in furnace waterwalls, thermal fatigue cracking induced by waterlances and water cannons, superheater-reheater corrosion, and erosion in fluidized-bed boilers.

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.

Managing corrosion continues to be a challenge for operators of modern boilers worldwide. This chapter addresses the corrosion-related problems that can occur in boilers burning municipal solid waste (MSW). It describes corrosion mechanisms associated with different environments and alloys. It also discusses corrosion protection methods for furnace waterwalls and superheater tubes in waste-to-energy boilers.

Black liquor recovery boilers are an integral part of the kraft pulping process used in paper mills. Besides recovering chemicals for reuse, they also produce process steam. High operating temperatures and exposure to process chemicals and combustion byproducts make recovery boilers susceptible to corrosion. This chapter describes some of the problems that the pulp and paper industry has solved as well as ongoing issues and concerns. It includes an in-depth review of 304L cladding failures involving coextruded composite tubes used as floor tunes in the lower furnace, as superheater tubes, and for other purposes such as smelt openings. It provides detailed images showing cracks on the outer surfaces of the tubes and explains where the tubes were used and how they were operated.

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.