Corrosion of metallic materials is governed by electrochemical kinetics, so that the general concepts developed for studying electrochemical reaction mechanisms may be applied to corrosion. This article presents the fundamental aspects of electrode kinetics. The processes of charge transfer taking place at the electrode interface within the double layer and of mass transport at the vicinity of the electrode surface are discussed. The article describes the corrosion processes, which involve anodic and cathodic reactions at specific electrode sites. Some experimental methods for devising a reliable reaction model are detailed. The article explains some reaction mechanisms for cathodic and anodic processes to illustrate the great variety of reaction mechanisms occurring at the electrode interface.

Electrochemical, or electrode, reactions occur with charge transfer between neutral or ionic reactants and a conducting material called the electrode. This article discusses cathodic reactions that result in reduction and anodic reactions that result in oxidation. It reviews the effects of an electric field near an electrode and illustrates the solvation of ions in metal-aqueous solution.

This article provides a general introduction to the kinetics of aqueous corrosion with an emphasis on electrochemical principles. It describes the thermodynamic basis for corrosion by determining the equilibrium potentials of electrochemical reactions from the Nernst equation. A corrosion process can be controlled by the electronic conductivity of passive films when the cathodic reaction occurs on the surface of the film and by activation control of corrosion. Passivation becomes thermodynamically possible when the corrosion potential exceeds the potential corresponding to the equilibrium between a metal and one of its oxides/hydroxides. The article schematically illustrates a current-potential or polarization curve for an anodic process.

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.

Principles of metallic corrosion play a fundamental role in developing industrial processes that employ corrosion for constructive purposes. This article examines the changes in kinetics that occur with differentially small potential changes around the equilibrium electrode potentials of two reversible electrodes, such as copper and silver electrodes, in an electrochemical system. It provides a schematic illustration of a reversible cell with copper and silver electrodes to determine a reversible cell potential between the electrodes. An electrode becomes irreversible when the electrode reactions are displaced from equilibrium and the electrode potential is no longer at the equilibrium potential. The article describes irreversible cell potential by using galvanic cells, electrolytic cells, and corrosion cells.

The electrode potential is one of the most important parameters in the thermodynamics and kinetics of corrosion. This article discusses the fundamentals of electrode potentials and illustrates the thermodynamics of chemical equilibria by using the hydrogen potential scale and the Nernst equation. It describes galvanic cell reactions and corrosion reactions in an aqueous solution in an electrochemical cell. The article explores the most common cathodic reactions encountered in metallic corrosion in aqueous systems. The reactions included are proton reduction, water reduction, reduction of dissolved oxygen, metal ion reduction, and metal deposition. The article also presents the standard equilibrium potentials measured at 25 deg C relative to a standard hydrogen electrode for various metal-ion electrodes in a tabular form.

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

This article examines constructive corrosion that occurs in power-generating devices, specifically batteries. It discusses the kinetic aspects of constructive corrosion in batteries and provides examples to illustrate how the kinetics of a corrosion process varies among different battery systems. The article illustrates the constructive roles played by corrosion at anodes in batteries through the use of a zinc anode in a mercury battery and a lithium metal anode in a rechargeable lithium battery. It also outlines the destructive role played by corrosion by illustrating shelf reactions in zinc-carbon batteries and lead grid corrosion in lead-acid batteries.

Electropolishing is an electrochemical process that involves anodic dissolution of a metal specimen (anode electrode) in an electrolytic cell. This article reviews the two-electrode and three-electrode systems for electropolishing. It presents the equations of anodic reactions and the selection criteria of electrolyte for electropolishing. The article also describes the mechanism of electropolishing and the effect of electropolishing on properties of metals.

This article reviews the types of passivity and presents tactics that employ passivity to control corrosion. Thermodynamics provides a guide to the conditions under which passivation becomes possible. A valuable guide to thermodynamics is the potential-pH diagram and the Pourbaix diagram. The article presents a potential-pH diagram for the iron-water system and an illustration of an idealized anodic polarization curve for a metal surface, which serves as a basis for describing the kinetics of passivation. It discusses five properties of passive films: thickness, composition, structure, electronic properties, and mechanical properties. The article outlines three possible processes that can form passive films: direct film formation, dissolution precipitation, and anodic oxidation of metal ions in solution. It describes the breakdown of the passive film using various models and highlighting the effect of alloy composition and structure.

Dealloying is a corrosion process in which one or more elements are selectively dissolved, leaving behind a porous residue of the remaining elements. This article describes the dealloying in various systems, namely, dezincification, graphitic corrosion, dealuminification, and noble metal alloys dealloying. The current-potential behavior of a binary alloy undergoing selective dissolution is reviewed. The article highlights the four mechanisms required for the formation of porous metals: ionization-redeposition, surface diffusion, volume diffusion, and percolation model of selective dissolution.

This article addresses electrochemical methods for instantaneous rate determination and threshold determination as well as nonelectrochemical methods that can determine incremental or cumulative rates of corrosion. Electrochemical methods for the study of galvanic corrosion rates and localized corrosion and evaluation of corrosion rates under paints are also discussed. The article describes nonelectrochemical methods that can determine incremental or cumulative rates of corrosion. Methods presented include polarization methods, polarization resistance methods, electrochemical impedance methods, frequency modulation methods, electrochemical noise resistance, potential probe methods, cyclic potentiodynamic polarization methods, potentiostatic and galvanostatic methods, electrochemical noise (EN) methods, scratch-repassivation method, and electrochemical impedance spectroscopy (EIS) techniques. Gravimetric determination of mass loss, electrical-resistance methods, magnetic methods, quartz crystal microbalance method, solution analysis methods, and metrological methods are nonelectrochemical methods. The article presents an electrochemical test that examines the susceptibility of stainless steel alloys to intergranular corrosion.

This article provides a background of the complex relationship between titanium and its alloys with aqueous environments, which is dictated by the presence of a passivating oxide film. It describes the corrosion vulnerability of titanium and titanium oxides by the classification of oxide failure mechanisms. The mechanisms are spatially localized oxide film breakdown by the ingress of aggressive anions; spatially local or homogenous chemical dissolution of the oxide in a strong reducing-acid environment; and mechanical disruptions or depassivation such as scratching, abrading, or fretting. Titanium alloys can be classified into three primary groups such as titanium alloys with hexagonal close-packed crystallographic structure; beta titanium alloys with body-centered cubic crystallographic structures; and alpha + beta titanium alloys including near-alpha and near-beta titanium alloys. The article also illustrates the effects of alloying on active anodic corrosion of titanium and repassivation behavior of titanium and titanium-base alloys.

This article reviews general corrosion of uranium and its alloys under atmospheric and aqueous exposure as well as with gaseous environments. It describes the dependence of uranium and uranium alloy corrosion on microstructure, alloying, solution chemistry, and temperature as well as galvanic interactions between uranium, its alloys, and other metals. The article provides information on the atmospheric corrosion of uranium based on oxidation in dry air or oxygen, water vapor, and oxygen-water vapor mixtures depending upon particular storage conditions. The mechanism and morphology of hydride corrosion of uranium are discussed. The article provides information on environmentally assisted cracking, protective coatings, and surface modification of uranium and its alloys. It also summarizes the environmental, safety, and health considerations for their use.

This article presents common conventions and definitions in corrosion, electrochemical cells, cathodic protection (CP), electricity, and oxidation. Evans diagrams for impressed current CP in neutral or basic environment and galvanic or sacrificial CP, in both neutral or basic environment and acidic environment, are illustrated.

This article focuses on the pack-cementation coatings, in particular, halide-activated pack cementation coatings on nickel alloys. It also describes the thermodynamics and kinetics of, and simultaneous deposition of various types of, pack cementation processes. These include pack aluminizing, chromizing, and siliconizing.

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.

The interaction of an implant with the human body environment may result in degradation of the implant, called corrosion. This article discusses the corrosion testing of metallic implants and implant materials. The corrosion environments for medical implants are the extracellular human body fluids, very complex solutions containing electrolytes and nonelectrolytes, inorganic and organic constituents, and gases. The article describes the fundamentals of electrochemical corrosion testing and provides a brief discussion on various types of corrosion tests. It illustrates corrosion current density determination by Tafel extrapolation, potentiodynamic measurement of the polarization resistance, electrochemical impedance measurement, and potentiostatic deaeration. Tests combining corrosion and mechanical forces, such as fretting corrosion tests, environment-assisted cracking tests, and ion-leaching tests are also discussed.

Chemical-mechanical planarization (CMP) of metals is described as mechanically accelerated corrosion, erosion corrosion, or metallic corrosion enhanced by wear. This article reviews the history, process, chemistry, electrochemistry, and defect issues for CMP. It provides an overview of CMP through a schematic illustration of CMP process equipment. The applications of CMP to tungsten and copper alloys are of prime interest in the semiconductor industry. The article discusses copper CMP and tungsten CMP in detail and analyzes polishing mechanism during CMP by application of direct current potentiodynamic polarization and alternating current impedance measurements. It concludes with information on chemically induced defects such as pitting corrosion, galvanic corrosion, and chemical etching.

This article provides an overview of the degradation of metals and alloys in aqueous systems. The importance of the hydrogen ion lies in its ability to interact with an alloy surface. The article describes the effects of various conditions of pH on corrosion including strongly acid conditions, near-neutral conditions, and strongly basic conditions as well as the effects of temperature on corrosion. The influence of the fluid flow rate on corrosion depends on the alloy, fluid components, fluid physical properties, geometry in which the fluid is contained, and corrosion mechanism. The article discusses the influence of fluid flow rate through specific examples. It concludes with information on how the concentration of dissolved species works with other variables to influence corrosion behavior.