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.

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.

This chapter discusses the principles and procedures of electrochemical measurements used to investigate corrosion behaviors. It begins by presenting a diagram of a basic potentiostatic circuit, which consists of a working electrode and an auxiliary or counter electrode suspended in an electrolytic solution. It describes how corrosion potentials and current densities are measured and explains how to deal with various sources of error. It also explains how electrochemical impedance measurements are used and describes the underlying theory and procedures in some detail.

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.

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 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.

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 covers the corrosion behavior of beryllium in aqueous environments. It describes the chemical reactions that drive the corrosion process, the conditions required for equilibrium, and the factors that affect corrosion resistance. It discusses the stability of the native oxides that form on the surface of beryllium and their ability to withstand acids, bases, and corrosive agents found in rain and seawater. It explains how carbides, inclusions, ions, and impurities contribute to corrosion damage, particularly pitting, and how corrosion reduces the ductility and fracture strength of certain beryllium alloys.

This appendix is a compilation of terms and definitions related to corrosion.

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 provides a detailed account of cathodic protection. It begins by discussing the fundamentals of cathodic protection followed by a description of the various types of cathodic protection. It then describes the origins, types, and alleged failures of cathodic protection criteria. This is followed by a section providing information on anode materials that are used for cathodic protection applications. General guidelines for designing the cathodic protection systems are also listed. Finally, the chapter presents various examples on cathodic protection of steel structures. The examples are selected to familiarize the design engineer with the steps to follow in selecting a specific corrosion-control method.

This chapter concentrates on the better-known and widely studied phenomenon of pitting corrosion of passive metals. The discussion focuses on different parameters that influence pitting corrosion, namely environment, metal composition, potential, temperature, surface condition, and inhibitors. It also provides information on various stages of pitting: passive film breakdown, metastable pitting, pit growth, and pit stifling or death.

This chapter is a detailed study of the localized corrosion behavior of steel, copper, and aluminum alloys. It applies the basic principles of electrochemistry, as well as materials science and solid and fluid mechanics, to explain the causes and effects of pitting, crevice corrosion, stress corrosion cracking, and corrosion fatigue. It describes the underlying mechanisms associated with each process and how they relate to the microstructure of the metal or alloy, the physical condition of the surface, and other factors such as the coupling of the metal to a dissimilar metal or surface film.