A potential pH diagram is a graphical representation of the relations, derived from the Nernst equation, between the pH and the equilibrium potentials (E) of the most probable electrochemical reactions occurring in a solution containing a specific element. This article describes three types of reactions for calculation and construction of E-pH diagrams: electrochemical reactions of pure charge (electron) transfer; reactions involving both electron and solvated proton transfer; and acid-base reactions of pure solvated proton transfer. It illustrates the practical use of E-pH diagrams for temperature aqueous solutions and adsorbed species and in prediction of corrosion of nickel and copper.

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.

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.

Crevice corrosion involves three fundamental types of processes such as electrochemical reactions, homogeneous chemical reactions, and mass transport. This article describes the critical factors of crevice corrosion, including crevice geometry, material, environment, crevice corrosion stifling, and pitting relationships. It explains the crevice corrosion of stainless steel, nickel alloys, aluminum alloys, and titanium alloys with examples. The article reviews the types of testing methods that have been developed for differentiating and ranking the resistance of alloys toward crevice corrosion. It also presents the strategies for the prevention of crevice corrosion or lessening its effects, such as design awareness, use of inhibitors, and electrochemical control methods.

Electrochemical refining is the purification process for producing commercially pure metals from crude metals. This article describes the principles of electrochemical reactions. It discusses the physical properties of the basic components of electrochemical refining cell. The article also explains the engineering considerations required in the refining process. Theoretical and technological principles of electrochemical refining are illustrated, with examples.

This article contains tables that list standard reduction potentials for electrochemical reactions. The first table lists reactions alphabetically by element of interest. The second table is ranked by potential value. Potential is measured versus the Standard Hydrogen Electrode which has a value of 0.0000 V. Reactions with more than one voltage indicate that results have not been reconciled. Parenthetical materials not needed to balance reactions are catalysts.

This article describes dental alloy compositions and its properties. It discusses the safety and efficacy considerations of dental alloy devices. The article defines and compares interstitial fluid and oral fluid environments. Artificial solutions developed for the testing and evaluation of dental materials are summarized. The article examines the effects of restoration contact on electrochemical parameters and reviews the concentration cells developed by dental alloy-environment electrochemical reactions. The composition and characterization of biofilms, corrosion products, and other debris that deposit on dental material surfaces are discussed. The article evaluates the types of alloys available for dental applications, including direct filling alloys, crown and bridge alloys, partial denture alloys, porcelain fused to metal alloys, wrought wire alloys, soldering alloys, and implant alloys. The effects of composition and microstructure on the corrosion of each alloy group are also discussed. The article concludes with information on the tarnishing and corrosion behavior of these alloys.

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.

Corrosion of metals is defined as deterioration caused by chemical or electrochemical reaction of the metal with its environment. This article provides information on corrosion of iron and steel by aqueous and nonaqueous media. It discusses the corrosive environments of carbon and alloy steels, namely atmospheric corrosion, soil corrosion, corrosion in fresh water and seawater. The article describes the corrosion process in concrete, which tends to create conditions that increase the rate of attack. The focus is on the stress-corrosion cracking of steels; an environmentally induced crack propagation that results from the combined interaction of mechanical stress and corrosion reactions. The article tabulates a guide on corrosion prevention for carbon steels in various environments. It also discusses protection methods of steel from corrosion, including coatings, such as temporary protection, cleaning, hot dip coating, electroplating, thermal spray coatings, conversion coatings, thin organic coatings, and inhibitors.

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 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.

This article describes the Bayer process for the purification of alumina. The process includes four major stages: digestion, clarification, precipitation, and calcination. The article discusses the aluminum electrolytic process in terms of aluminum electrolysis cell design, magnetohydrodynamic forces, and cathode lining. It reviews the electrochemical reactions and thermodynamics for aluminum electrolysis standard Gibbs. The article also describes the cell operations and cell stability, as well as the key indicators of cell performance. It schematically illustrates the typical costs producing aluminum in an aluminum smelter. The article also discusses various environmental issues, such as fluoride recovery; perfluorocarbons, polycyclic aromatic hydrocarbons, and sulfur emissions; spent pot lining; and development of inert anodes and CO2 emissions.

Corrosion is the electrochemical reaction of a material and its environment. This article addresses those forms of corrosion that contribute directly to the failure of metal parts or that render them susceptible to failure by some other mechanism. Various forms of corrosion covered are galvanic corrosion, uniform corrosion, pitting, crevice corrosion, intergranular corrosion, selective leaching, and velocity-affected corrosion. In particular, mechanisms of corrosive attack for specific forms of corrosion, as well as evaluation and factors contributing to these forms, are described. These reviews of corrosion forms and mechanisms are intended to assist the reader in developing an understanding of the underlying principles of corrosion; acquiring such an understanding is the first step in recognizing and analyzing corrosion-related failures and in formulating preventive measures.

This article is a compilation of tables that list the standard reduction potentials for electrochemical reactions alphabetically by element of interest and potential value.

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 discusses the principles of corrosion and the basis of the various prevention measures that can be taken for different corrosion modes. It describes aqueous corrosion phenomena in terms of the electrochemical reactions that occur at the metal-environment interface. The article explains the specific forms of corrosion, including general corrosion, localized attack, and environmentally assisted cracking. It provides a discussion on the engineering aspects of design that can, without due care and attention, precipitate unexpected premature failure. The article reviews ways to improve corrosion awareness and prevent corrosion/degradation. It describes a life prediction method with an example of environmental degradation in light-water nuclear reactors. The article concludes with a discussion on the validation of life-prediction algorithms and their applications.

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 focuses on the testing and typical corrosion behavior of coating-substrate systems in aqueous solutions and humid aggressive atmospheres. It includes a short review of the fundamentals of corrosion, followed by a discussion of specific system behavior, electrochemical and laboratory accelerated tests, and simulated service tests. The article also contains examples of different types of corrosion damage and presents guidelines for improving corrosion resistance.