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.

When metal is exposed to an oxidizing gas at elevated temperature, corrosion can occur by direct reaction with the gas, without the need for the presence of a liquid electrolyte. This type of corrosion is referred to as high-temperature gaseous corrosion. This article describes the various forms of high-temperature gaseous corrosion, namely, high-temperature oxidation, sulfidation, carburization, corrosion by hydrogen, and hot corrosion.

This article provides a discussion on the mechanisms of wear and their interactions with gaseous corrosion. The wear mechanisms include abrasive, erosive, fretting, and sliding. The measurement of degradation on combustion walls in coal-fired boilers is discussed. The article concludes with information on the common coating techniques used for wear-corrosion control.

Metals can react chemically with oxygen when exposed to air. Essential to an understanding of the gaseous corrosion of a metal are the crystal structure and the molar volume of the metal on which the oxide builds, both of which may affect growth stresses in the oxide. This article presents crystal structures and thermal properties of pure metals and oxides in a tabular form. The free energy of reaction, which describes the oxidation process of a pure divalent metal, is presented. The article illustrates the Richardson-Jeffes diagram, which is used in the determination of the standard Gibbs energy change of formation of oxides and the corresponding dissociation pressures of the oxides as a function of temperature. It demonstrates the Kellogg diagram which shows stability range in more complicated multioxidant systems. The article explains the determination of partial pressures of gas mixtures and partial pressures of volatile oxidation products.

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.