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.

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.

Electrode potential is a key parameter in the thermodynamic and kinetic processes that drive aqueous corrosion. This article discusses the complexities associated with measuring electrode potential and explains where and how to use reference electrodes to improve measurement accuracy. It describes a three-electrode approach that compensates for measurement error stemming from nonequilibrium conditions. It also examines electrode materials and behaviors and offers insights on selection and operating conditions.

Overpotential is the current-producing potential difference between a nonequilibrium electrode potential and its corresponding equilibrium value for an electrode reaction. This article provides information on the overpotential of an electrode reaction. It contains a table that lists the values based on the electrode reaction. Because overpotential is a kinetic parameter and depends on current density, overpotential values presented are for a specific current density.

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 describes the ideal performance of various low-temperature and high-temperature fuel cells that depends on the electrochemical reactions that occur between different fuels and oxygen. Low-temperature fuel cells, such as polymer electrolyte, alkaline, and phosphoric acid, and high-temperature fuel cells, such as molten carbonate and solid oxide, are discussed. The article contains tables that provide information on the evolution of cell-component technology for these fuel cells. It concludes with information on the advantages and limitations of the fuel cells.

Multiple-layer alloy electrodeposition involves the formation of an inhomogeneous alloy consisting of lamellae of different composition. This article reviews the process description, engineering parameters, characterization, and applications of multiple-layer alloys. Pulsed-current plating and pulsed-potential plating are also discussed.

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.

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 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 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.

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.

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 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 overviews the classification of welding processes and the key process embodiments for joining by various fusion welding processes: fusion welding with chemical sources for heating; fusion welding with electrical energy sources, such as arc welding or resistance welding; and fusion welding with directed energy sources, such as laser welding, electron beam welding. The article reviews the different types of nonfusion welding processes, regardless of the particular energy source, which is usually mechanical but can be chemical, and related subprocesses of brazing and soldering.

Fusion-based additive manufacturing (AM) processes rely on the formation of a metallurgical bond between a substrate and a feedstock material. Energy sources employed in the fusion AM process include conventional arcs, lasers, and electron beams. Each of these sources is discussed, with an emphasis on their principles of operation, key processing variables, and the influence of each source on the transfer of heat and material. Common energy sources used for metals AM processes, particularly powder-bed fusion and directed-energy deposition, are also discussed. Brief sections at the end of the article discuss the factors dictating the choice of each of these energy sources and provide information on alternative sources of AM.

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.

Fluxes are added to the welding environment to improve arc stability, to provide a slag, to add alloying elements, and to refine the weld pool. This article describes the effect of oxygen that directly reacts with alloying elements to alter their effective role by reducing hardenability, promoting porosity, and producing inclusions. It proposes basicity index for welding as a measure of expected weld metal cleanliness and mechanical properties. The article discusses alloy modification in terms of slipping and binding agents, slag formation, and slag detachability. It reviews the types of fluxes for different arc welding processes, such as shielded metal arc welding (SMAW), flux-cored arc welding (FCAW), and submerged arc welding (SAW).

This article focuses on the corrosion fatigue testing of steel in high-temperature water and discusses critical experimental issues associated with it. It provides information on the fundamental aspects of environmental crack advancement in general. The article explains the concepts and role of environmentally assisted crack growth in corrosion fatigue. It also discusses the fatigue test methods, including crack initiation testing and crack propagation testing. The article describes the specific types and influence rankings of experimental variables in corrosion fatigue.