Corrosion involves chemical reactions in equilibrium that that are understood through principles of thermodynamics. In practice, the rate at which corrosion reactions occur is the most important consideration. This chapter deals with corrosion kinetics, which allows engineers to to understand rates of corrosion. The discussion covers two kinetic processes, namely electrode reactions at the cathode and anode and conduction of ions in the electrolyte. The chapter also provides information on passivation and its effect on polarization diagrams.

This chapter contains sample problems with worked solutions pertaining to the application of corrosion inhibitors. Correct answers require an understanding of potentiodynamic polarization scan (PDS) curves, the determination of corrosion current and inhibitor efficiency, and the development of a test plan to evaluate the long-term corrosion protection of a potential inhibitor.

Corrosion is a key subject for more or less all classes of alloys that fall within the broad definition of stainless steels because these alloys were developed with the intention of preventing corrosion. This chapter provides an introduction to the fundamentals of electrochemical theory as it pertains to corrosion resistance of stainless steels. The discussion provides an overview of electrochemical reactions, Faraday's law, the Nernst equation, galvanic versus electrochemical cells, corrosion tendency, and Pourbaix diagrams.

This chapter provides an introduction to various forms of corrosion, namely uniform corrosion, localized corrosion, mechanically assisted degradation, environmentally induced cracking, microbiologically influenced corrosion, and metallurgically influenced corrosion.

This chapter covers the engineering aspects of corrosion inhibitors and their effect on corrosion reactions. It explains how different metallic salts and heterocyclic compounds influence chemical reactions on metal surfaces exposed to corrosive media or environments. It describes how to evaluate inhibition efficiency through weight loss measurements, linear polarization resistance tests, electrochemical impedance spectroscopy, electrochemical noise monitoring, and surface analysis. It demonstrates the use of potentiodynamic polarization curves, Tafel extrapolations, equivalent circuit models, and various methods for characterizing corrosion damage and protective surface films. It also discusses typical applications, industry trends, and the emerging role of high-throughput experimentation, quantitative modeling, and machine learning in the development of cleaner and more effective corrosion inhibitors.

This chapter lays the groundwork for understanding electrode kinetics associated with corrosion. It presents a simple but useful theory relating kinetics to the polarization behavior of half-cell reactions. The theory is based on the observation that electrode potentials vary as a function of current density or charge transfer in a given area. The chapter explains how to measure and plot electrode potentials and currents and how to interpret the resulting polarization curves. It also discusses the effects of concentration gradients, explaining how they cause diffusion and, in some cases, produce changes in electrode potential.

This chapter discusses the principles of corrosion of metals in aqueous environments. The thermodynamics of aqueous corrosion is the subject of the first half of this chapter, which addresses concepts such as corrosion reactions and free-energy change, the relationship between free energy and electrochemical potential, the effect of ionic concentration on electrode potential, and the corrosion behavior of a metal based on its potential-pH diagram. The corrosion (potential-pH) behavior of iron, gold, copper, zinc, aluminum, and titanium are described. Understanding the kinetics of corrosion and the factors that control the rates of corrosion reactions requires examination of the concepts of polarization behavior and identification of the various forms of polarization in an electrochemical cell. These concepts, addressed in the remaining of this chapter, include anodic and cathodic reactions, the mixed-potential theory, and the exchange currents.

This chapter explores the behavior of stainless steel in media that promote corrosion. The forms of corrosion covered are uniform corrosion, atmospheric corrosion, localized corrosion, pitting corrosion, crevice corrosion, and grain boundary corrosion. The chapter discusses the influence of material and environmental variables on stress-corrosion cracking (SCC) and the mechanisms proposed for SCC in stainless steel, comparing the mechanism of SCC with hydrogen embrittlement. In addition, it provides information on biocorrosion and microbiologically induced corrosion in ambient aqueous environments.

This chapter familiarizes readers with the basic concepts of corrosion, discussing chemical reactions, ion transfer mechanisms, electrochemical processes and variables, and the formation of solid corrosion products. It presents a simple but effective teaching tool, the elementary electrochemical corrosion circuit, using it to explain how electric potential differences drive the corrosion process and how corrosion rates vary in proportion to current density. The chapter concludes with a discussion on the importance of corrosion products, such as oxides and hydroxides, and how their formation can be a major factor in controlling corrosion.

This chapter discusses the complex polarization characteristics of active-passive metals and addresses related problems in interpreting their corrosion behavior. It begins by presenting several experimentally derived polarization curves for iron, comparing and contrasting them with the iron-water Pourbaix diagram. It then explains how anodic polarization is extremely sensitive to the environment and, as a result, a reasonably complete curve for a given metal-environment system usually can only be inferred. It goes on to describe how such curves are constructed, demonstrating the procedures for a wide range of alloys and environments. The examples also show how factors such as alloy concentration, crystal lattice orientation, temperature, and dissolved oxygen affect corrosion behavior.

Gas-metal reactions can have a significant impact on metals and alloys, affecting their properties (during processing) and accelerating service failures, particularly in hot, corrosive environments. This chapter discusses the kinetics of gas-metal reactions and how they are driven by Gibbs energy changes. It plots the energy of formation for many important metal oxides and explains how to construct isothermal stability diagrams to analyze complex reactions involving metals, alloys, and gases containing more than one reactive component.

High-strength steels are susceptible to stress-corrosion cracking (SCC) even in moist air. This chapter identifies such steels and the applications where they are typically found. It provides information on crack growth kinetics and crack propagation models in which hydrogen embrittlement is the predominant mechanism. It explains how different application variables affect SCC, including loading mode, state of stress, type of steel, temperature, electrochemical potential, heat treatment, and deformation processes. It also compares SCC characteristics in different high-strength steels and discusses the influence of composition, steelmaking practice, and application environment.

This chapter discusses the effects of metallurgical variables on dealloying corrosion. It begins by describing the processes involved in dealloying of metal alloys in aqueous environments. This is followed by a discussion on the morphology of porous dealloyed structures below and above the critical potential. Some features experimentally observed for dealloying systems are then considered. The chapter concludes by briefly reviewing the proposed mechanisms for the formation of porous metals, namely ionization-redeposition mechanism, surface diffusion mechanism, volume diffusion mechanism, and percolation model of selective dissolution.

This chapter is dedicated mostly to the metallurgical effects on the corrosion behavior of corrosion-resistant alloys. It begins with a section describing the importance of alloying elements on the corrosion behavior of nickel alloys. The chapter considers the metallurgical effects of alloy composition for heat-resistant alloys, nickel corrosion-resistant alloys, and nickel-base alloys. This chapter also discusses the corrosion implications of changing the alloy microstructure via solid-state transformation, second-phase precipitation, or cold work. It concludes with a comparison of corrosion behavior between cast and wrought product forms.

This chapter describes the corrosion behavior of beryllium in gaseous atmospheres, including oxygen, nitrogen, carbon dioxide, and carbon monoxide. It also discusses the development of high-temperature corrosion-resistant beryllium alloys.

This chapter discusses some of the metallurgical factors that affect corrosion of weldments and describes a few considerations for selected nonferrous alloy systems: aluminum, titanium, tantalum, and nickel.

This chapter focuses on resistance characteristics and methods of protecting different forms of high-temperature gaseous corrosion, namely high-temperature oxidation, sulfidation, carburization, hydrogen effects, and hot corrosion.

This chapter develops a corrosion model that accounts for solution potentials and the effects of coupling between cathodic and anodic reactions. It begins by examining potential differences at various points (in the solution) along a path from the anode to the cathode area. It then presents a simple model of a galvanically coupled electrode, in which the metal is represented as an array of anode and cathode reaction surfaces. The chapter goes on to develop the related theory of mixed electrodes, showing how it can be used to predict corrosion rates based on measured potentials and current densities, polarization characteristics, and physical variables such as anode-to-cathode area ratios and fluid velocity. It also discusses the effect of corrosion inhibitors, galvanic coupling, and external currents, making extensive use of polarization curves.