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.

This article discusses two general mechanisms of corrosion in molten salts. One is the metal dissolution caused by the solubility of the metal in the melt. The second and most common mechanism is the oxidation of the metal to ions. Specific examples of the types of corrosion expected for the different metal-fused salt systems are also provided. The metal-fused salt systems include molten fluorides, chloride salts, molten nitrates, molten sulfates, hydroxide melts, and carbonate melts. The article concludes with information on prevention of molten salt corrosion.

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.

This article provides a discussion on the fundamentals of corrosion thermodynamics. The discussion focuses on electrochemical reactions, molten salt corrosion thermodynamics, and geochemical modeling.

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.

Molten salts, or fused salts, can cause corrosion by the solution of constituents of the container material, selective attack, pitting, electrochemical reactions, mass transport due to thermal gradients, and reaction of constituents and impurities of the molten salt with the container material. This article describes a test method performed using thermal convection loop for corrosion studies of molten salts. It discusses the purification of salts that are used in the Oak Ridge molten salt reactor experiment. The article also reviews the corrosion characteristics of nitrates/nitrites and fluoride salts with the aid of illustrations and equations.

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.

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 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 provides information on the thermodynamics and kinetics of high-temperature corrosion. The thermodynamics of high-temperature corrosion reactions reveals what reactions are possible under certain conditions and kinetics explains how fast these possible reactions will proceed. The article describes the diffusion process that plays a key role in oxidation and other gaseous reactions with metals. It discusses the development of stress in oxide layers. The article presents the sample preparation methods for high-temperature testing, and expounds the measurement methods of high-temperature degradation. It reviews a number of potential processes, which are responsible for high-temperature corrosion. The article details a wide range of coatings and coating processes for protecting components in a variety of operating conditions. It also discusses the testing methods used for materials at high temperatures, including furnace tests, burner rig testing, and thermogravimetric analysis, and the test methods conducted at high temperature and high pressure.

This article describes the dip brazing process and the principal types of furnaces used for molten-salt-bath dip-brazing applications. It provides information on equipment maintenance, which is divided into temperature control, control of the liquid, and maintenance of the vessel. The article presents the typical salts used for molten-salt dip brazing of carbon and low-alloy steels with selected filler metals in tabular form. It concludes with information on dip brazing of stainless steels, cast irons, and aluminum alloys and safety precautions of the process.

High temperature corrosion may occur in numerous environments and is affected by factors such as temperature, alloy or protective coating composition, time, and gas composition. This article explains a number of potential degradation processes, namely, oxidation, carburization and metal dusting, sulfidation, hot corrosion, chloridation, hydrogen interactions, molten metals, molten salts, and aging reactions including sensitization, stress-corrosion cracking, and corrosion fatigue. It concludes with a discussion on various protective coatings, such as aluminide coatings, overlay coatings, thermal barrier coatings, and ceramic coatings.

This article examines the high-temperature oxidation of silica-forming ceramics under constant temperature and cyclic conditions. The effects of water vapor, impurities, and molten salts are discussed. The article describes the oxidation and corrosion of silica-forming composites, oxide ceramics, non-silica forming nitrides, carbides, and borides. The performance of environmental barrier coatings by material type is also discussed. The article also explains the effects of oxidation and corrosion on the mechanical properties of ceramic-matrix composites. It concludes with information on high-temperature applications, wear properties, and the microscopic analyses of advanced ceramics.

Molten salt baths are anhydrous, fused chemical baths used at elevated temperatures for a variety of industrial cleaning applications. This article discusses their applications in paint stripping, polymer removal, casting cleaning, glass removal, and plasma/flame spray removal. It provides an overview of the basic design and safety considerations of the salt bath equipment and describes the environmental impact of molten salt bath cleaning.

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.

Cast irons, like steels, are iron-carbon alloys but with higher carbon levels than steels to take advantage of eutectic solidification in the binary iron-carbon system. This article introduces the solid-state heat treatment of iron castings and describes the various processes of heat treatment of cast iron. It provides information on stress relieving, annealing, normalizing, through hardening, and surface hardening of these castings. The article discusses general considerations for the heat treatment of cast iron. Cast irons are occasionally nitrided for various applications with the aim of enhancing surface hardness and corrosion resistance of the products. The article describes molten salt bath cyaniding and ion nitriding of cast iron.

Although stainless steel is naturally passivated by exposure to air and other oxidizers, additional surface treatments are needed to prevent corrosion. Passivation, pickling, electropolishing, and mechanical cleaning are important surface treatments for the successful performance of stainless steel. This article describes the surface treatment of stainless steels including abrasive blast cleaning, acid pickling, salt bath descaling, passivation treatments, electropolishing, and the necessary coating processes involved. It also describes the surface treatment of heat-resistant alloys including metallic contaminant removal, tarnish removal, oxide and scale removal, finishing, and coating processes.