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 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 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 thorough introduction to the electrochemical thermodynamics that govern electrode reactions associated with corrosion. It begins with a review of the thermodynamic criteria for the stability of chemical reactions based on Gibbs free energy and explains how energies of formation are determined using the oxidation of iron as an example. It then considers how iron reacts with hydrochloric acid, explaining how it can be expressed as two half reactions modeled as electrodes in an electrochemical cell. It goes on to describe the chemical reactions occurring at each electrode, accounting for different variables, mechanisms, and electrochemical effects. The chapter concludes with an in-depth review of Pourbaix diagrams, explaining what they reveal about the stability of metal-water systems and the formation of corrosion products.

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 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.

This appendix is a comprehensive collection of selected sources related to corrosion properties of materials and corrosion testing.

This chapter provides information on the selection of steel and the design of its heat treatment. It also discusses the purpose of this book.

This chapter describes the two types of Time-Temperature-Transformation (TTT) diagrams used and outlines the methods of determining them. As a precursor to the examination of the decomposition of austenite, it first reviews the phases and microconstituents found in steels. This includes a presentation of the iron-carbon phase diagram and the equilibrium phases. The chapter also covers the common microconstituents that form in steels, including the nomenclature used to describe them. The chapter provides a comparison of isothermal and continuous cooling TTT diagrams. These diagrams are affected by the carbon and alloy content and by the prior austenite grain size, and the way in which these factors affect them is examined.

This chapter first examines the tempering behavior of plain carbon steels and then that of alloy steels. Next, some correlations are examined which allow estimations of the tempered hardness from the chemical compositions, tempering temperature and tempering time. The chapter then describes the effect of tempering on the mechanical properties of plain carbon steels and the microstructure of plain carbon steels. It shows examples of the structure of plain carbon steels. Additionally, the chapter explains the stages and kinetics of tempering in alloy steels and plain carbon steels. It also describes some methods of estimating the hardness. Finally, the chapter discusses the important problem of temper embrittlement.

This chapter contains problems that illustrate the calculation or determination of such items as ideal critical diameter, the Jominy curve, and the severity of quench by methods. It presents solutions for the calculation of the effect of prior austenite grain size, carbon content, chromium content, and molybdenum content on ideal critical diameter. The chapter also contains solutions for calculation of Jominy curves and determination of minimum hardness of quenched steels, tempered hardness, ideal critical diameter, severity of quench, heat treatment, and effect of tempering during heat-up to tempering temperature.

This chapter discusses the method for calculating hardenability from composition. It contains tables listing multiplying factors, carbon content, initial hardness, and 50% martensite hardness. The tables also list Jominy distance for 50% martensite vs. DI (in. and mm), boron factors vs. % carbon and alloy factor, and distance hardness dividing factors for non-boron and boron steels (in. and mm).

This appendix contains a table listing the factors for calculating the ideal critical diameter for steels as given in the ASTM standard A255-67.

This data sheet includes a select list of factors for converting customary English units to metric (SI) units.

This appendix contains metric energy conversions for J and ft-lb.

This appendix contains the metric stress or pressure readings (MPa or ksi) to be converted.

This appendix contains a temperature conversion table listing temperatures to be converted, along with degree Centigrade or Fahrenheit equivalent.

This appendix lists AISI-SAE system of designations for steels.