High-temperature corrosion can occur in numerous environments and is affected by various parameters such as temperature, alloy and protective coating compositions, stress, time, and gas composition. This article discusses the primary mechanisms of high-temperature corrosion, namely oxidation, carburization, metal dusting, nitridation, carbonitridation, sulfidation, and chloridation. Several other potential degradation processes, namely hot corrosion, hydrogen interactions, molten salts, aging, molten sand, erosion-corrosion, and environmental cracking, are discussed under boiler tube failures, molten salts for energy storage, and degradation and failures in gas turbines. The article describes the effects of environment on aero gas turbine engines and provides an overview of aging, diffusion, and interdiffusion phenomena. It also discusses the processes involved in high-temperature coatings that improve performance of superalloy.

This article reviews high-temperature corrosion of furnace parts used in heat-treating furnaces. It provides a comparison of cast and wrought materials in the context of their general considerations, advantages, and applications. The article provides information on the heat-resistant alloys used for parts that go through the furnaces, including trays, fixtures, conveyor chains and belts, and quenching fixtures and parts, and the parts that remain in the furnace such as combustion tubes, radiant tubes, burners, thermowells, roller and skid rails, baskets, pots, retorts, muffles, and drive and idler drums. The article also reviews the material characteristics of silicon/silicon carbide composite and reaction-bonded silicon carbide as used in radiant tubes.

High-temperature exposure of materials occurs in many applications such as power plants (coal, oil, natural gas, and nuclear), land-based gas turbine and diesel engines, gas turbine engines for aircraft, marine gas turbine engines for shipboard use, waste incineration, high-temperature fuel cells, and missile components. This article discusses high-temperature corrosion in boilers, diesel engines, gas turbines, and waste incinerators. Boilers are affected by stress rupture failures, waterside corrosion failures, fireside corrosion failures, and environmental cracking failures. Contamination of combustion fuel in diesel engines can cause high-temperature corrosion. Gas turbine engines are affected by hot corrosion. Refractory-lined incinerators and alloy-lined incinerators are discussed. The article provides case studies for each component failure.

Steel automotive exhaust systems suffer from various forms of corrosion. This article illustrates exhaust system components with typical upper metal skin temperatures and alloys of construction. It discusses high-temperature corrosion of automotive exhaust systems, including oxidation, hot salt attack, and thermal fatigue. The article describes the various forms of corrosion which occur at the cold end of an exhaust system. The forms of cold end exhaust corrosion, including condensate pitting corrosion, exterior salt pitting, crevice corrosion, intergranular corrosion, and galvanic corrosion.

The presence of certain impurities in coal and oil is responsible for the majority of fireside corrosion experienced in utility boilers. In coal, the primary impurities are sulfur, alkali metals, and chlorine. The most detrimental impurities in fuel oil are vanadium, sodium, sulfur, and chlorine. This article describes the two categories of fireside corrosion based on location in the furnace: waterwall corrosion in the lower furnace and fuel ash corrosion of superheaters and reheaters in the upper furnace. It discusses prevention methods, including changes to operating parameters and application of protective cladding or coatings.

This article describes the corrosion modes in a waste-to-energy boiler. It discusses the corrosion protection and alloy performance with an emphasis on two main areas of the boiler: furnace water walls and super heaters.

The corrosion issues in the compressor, combustor and turbine sections of industrial gas turbines used in steam production generally depend on the quality of the fuel, air, and water used in the engine than on the specific industrial application. This article focuses on the forms of corrosion and their preventive measures in the compressor, combustor and turbine sections of a steam turbine. The compressor section mainly suffers from aqueous corrosion; while in case of the combustor and turbine sections, which are made of nickel-base superalloys, high-temperature environmental attack in the form of high-temperature oxidation and hot corrosion are predominant. The effect of high-temperature oxidation and hot corrosion on the mechanical properties of superalloys is also discussed.

Understanding the high-temperature corrosion behavior of alloys is an important step toward the selection of appropriate alloys for process equipment. This article briefly describes the high-temperature corrosion modes that are frequently encountered in the chemical process industry. These modes include oxidation, carburization, metal dusting, nitridation, halogen corrosion, and sulfidation.

This article focuses on high-temperature corrosion in synthetic gas (syngas) coolers. Extensive laboratory corrosion studies on both model and commercial alloys are summarized. The article describes the material selection criteria for long-term performance of materials in service. It provides information on the fuels with chlorine contents used in gasification plants.

The high-temperature corrosion processes that are most frequently responsible for the degradation of furnace accessories are oxidation, carburization, decarburization, sulfidation, molten-salt corrosion, and molten-metal corrosion. This article discusses each corrosion process, along with the corrosion behavior of important engineering alloys. It describes the corrosion of plating, anodizing, and parts of pickling equipment such as tanks, wirings and bus bars, racks, anode splines, pumps, and heaters.

This article presents the primary considerations and mechanisms for corrosion and explains how they are involved in the selection of materials for process equipment in refineries and petrochemical plants. It discusses the material selection criteria for a number of ferrous and nonferrous alloys used in petroleum refining and petrochemical applications. The article reviews the mechanical properties, fabricability, and corrosion resistance of refinery steels. It describes low- and high-temperature corrosion, hydrogen embrittlement, and cracking such as stress-corrosion, sulfide stress, and stress-oriented hydrogen-induced cracking. The article considers hydrogen attack, corrosion fatigue, and liquid metal embrittlement and the methods of combating them. It explains the causes of velocity-accelerated corrosion and erosion-corrosion. The article summarizes some corrective measures that can be implemented to control corrosion. The applicable standards for materials used in corrosive service conditions in upstream and downstream petroleum service are presented in a tabular form.

This article reviews the corrosion behavior in various environments for seven important nickel alloy families: commercially pure nickel, Ni-Cu, Ni-Mo, Ni-Cr, Ni-Cr-Mo, Ni-Cr-Fe, and Ni-Fe-Cr. It examines the behavior of nickel alloys in corrosive media found in industrial settings. The corrosive media include: hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, nitric acid, organic acids, salts, seawater, and alkalis. The modes of high-temperature corrosion include oxidation, carburization, metal dusting, sulfidation, nitridation, corrosion by halogens, and corrosion by molten salts. Applications where the corrosion properties of nickel alloys are important factors in materials selection include the petroleum, chemical, and electrical power industries. Most nickel alloys are much more resistant than the stainless steels to reducing acids, such as hydrochloric, and some are extremely resistant to the chloride-induced phenomena of pitting, crevice attack, and stress-corrosion cracking (to which the stainless steels are susceptible). Nickel alloys are also among the few metallic materials able to cope with hot hydrofluoric acid. The conditions where nickel alloys suffer environmentally assisted cracking are highly specific and therefore avoidable by proper design of the industrial components.

This article addresses the cobalt and cobalt-base alloys most suited for aqueous environments and those suited for high temperatures. The performance of cobalt alloys in aqueous environments encountered in commercial applications is discussed. The article provides information on the environmental cracking resistance of the cobalt alloys. Three welding processes that are used for hardfacing with the high-carbon Co-Cr-W alloys, namely, oxyacetylene, gas tungsten arc, and plasma-transferred arc are also discussed. The article examines the effects of various modes of high-temperature corrosion. It describes the applications and fabrication of cobalt alloys for high-temperature service.

This article reviews the corrosion behavior of intermetallics for the modeling of the corrosion processes and for devising a strategy to create corrosion protective systems through alloy and coating design. Thermodynamic principles in the context of high-temperature corrosion and information on oxidation; sulfidation; hot corrosion of NiAl-, FeAl-, and TiAl-based intermetallics; and silicides are included. The article explores the thermodynamic consideration, ordering influencing kinetics, stress-cracking corrosion, and hydrogen embrittlement of aqueous corrosion. It also explains the practical issues dealing with the corrosion problems.

This article describes the specific features and mechanisms of oxidation in thermal spray coatings. It discusses the two forms of hot corrosion in sulfur-containing combustion, namely high-temperature hot corrosion and low-temperature hot corrosion. The article reviews the behavior of corrosion-resistant coatings in boilers. The effects of high-temperature corrosion in waste incinerators are detailed. The article also examines the effects of erosion-corrosion in fluidized bed combustion boilers.

This article provides a summary of the concepts discussed in the articles under the Section “Fundamentals of Corrosion” in ASM Handbook, Volume 13A: Corrosion: Fundamentals, Testing, and Protection. In this section, the thermodynamic aspects of corrosion are descried first followed by a group of articles discussing the fundamentals of aqueous corrosion kinetics. The fundamentals of gaseous corrosion are addressed next. The fundamental electrochemical reactions of corrosion and their uses are finally described.

This article examines the characteristics and behavior of scale produced by various types of oxidation. The basic models, concepts, processes, and open questions for high-temperature gaseous corrosion are presented. The article describes the development of geometrically induced growth stresses, transformation stresses, and thermal stresses in oxide scales. It discusses the ways in which stresses can be relieved. The article provides information on catastrophic oxidation, internal oxidation, sulfidation, alloy oxidation, selective oxidation, and concurrent oxidation. It illustrates the relationships between scale morphologies on binary alloys and concludes with a discussion on metal dusting and chlorine corrosion.

This article discusses two approaches for determining gaseous corrosion rates, one based on indirect (discontinuous) measurements, the other based on direct (continuous) measurements. It explains how corrosion rate data can be obtained indirectly by measuring scale thickness, scale weight per unit surface area, loss of metal thickness, loss of material weight per unit surface area, or weight change of oxidant bonded in the scale per unit surface area as a function of time. It also describes several continuous methods, including volumetric measurements, the manometric method, and thermogravimetric analysis, and the conditions under which they can be used.

Metals and ceramics exposed to high-temperature salt solutions are susceptible to a form of corrosion caused by fused salts accumulating on unprotected surfaces. This article examines the electrochemistry of such hot corrosion processes, focusing on sodium sulfate systems generated by the combustion of fossil fuels. It explains how salt chemistry, including acid/base and oxidizing properties, affects corrosion rates and mechanisms. The article also provides information on electrochemical testing and explains how Pourbaix methods, normally associated with aqueous corrosion, can be used to study fused-salt corrosion.

Molten salts, in contrast to aqueous solutions in which an electrolyte (acid, base, salt) is dissolved in a molecular solvent, are essentially completely ionic. This article begins with an overview of the thermodynamics of cells and classification of electrodes for molten salts: reference electrodes and indicator electrodes. It explains that corrosion in molten salts can be caused by the solubility of the metal in the salt, particularly if the metal dissolves in its own chloride. The article describes the factors that affect the corrosion of titanium, namely, the titanium chloride content of the magnesium chloride melt, magnesium or sodium content, and oxygen content of the product. It concludes with a discussion on the oxygen activity in the titanium metal product.