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.

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.

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.

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.

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

This article provides an overview of the electrochemical nature of corrosion and analyzes corrosion-related failures. It describes corrosion failure analysis and discusses corrective and preventive approaches to mitigate corrosion-related failures of metals. These include: change in the environment; change in the alloy or heat treatment; change in design; use of galvanic protection; use of inhibitors; use of nonmetallic coatings and liners; application of metallic coatings; use of surface treatments, thermal spray, or other surface modifications; corrosion monitoring; and preventive maintenance.

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.