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 explains how the principles of chemical thermodynamics are used in the construction and interpretation of phase diagrams. After a brief review of the laws of thermodynamics, it describes the concept of Gibbs free energy and its application to transformations that occur in single-component and binary solid solutions. It then examines the relationship between the free energy of a solution and the chemical potentials of the individual components. It also explains how to account for the heat of mixing using quasi-chemical models, discusses the effect of interatomic bond energies and chemical potentials, and shows how the equilibrium state of an alloy can be obtained from free-energy curves.

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 provides a fundamental understanding of beryllium reduction thermodynamics as a prerequisite for subsequent chapters on extraction, chemical processing, and corrosion. It examines a number of reduction methods along with a potential refining process, highlighting the challenges encountered with each.

Oxidation usually dominates high-temperature corrosion reactions, but under certain conditions, some alloys may be affected by nitridation as well. This chapter explains why nitridation occurs and how it attacks various metals, in some cases, penetrating deeper than oxidation. It provides images and data describing the nitridation process and its effects on metals and alloys in high-temperature air as well as NH3-H2O, NH3 and H2-N2-NH3, and N2 environments. It also includes test data showing that nitridation is more severe in a nitrogen atmosphere than an ammonia environment at 1090 °C (2000 °F).

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.

Many scientific-technological advances depend critically on solid-state elastic properties, their magnitudes, and their responses to variables like stress and temperature. This chapter provides the definitions and descriptions of elastic constants and emphasizes five aspects of engineering-material solid-state elastic constants: general properties; interrelationships; relationships, especially thermodynamic to other physical properties; changes during cooling from ambient to near-zero temperature; and near-zero-temperature behavior.

This chapter provides an overview of a computational method, called CALPHAD, used for the study of phase equilibria in multicomponent systems. It describes the thermodynamic models and calculation techniques employed in the software and explains how it applies to complex alloys used in industry. It also provides examples showing how CALPHAD has been used to determine the formability of metallic glass, calculate the dilation of stainless steel during phase transformation, and predict the beta transus and approach curves of commercial titanium alloys.

This chapter explains the distinction between materials and matter through the concept of microstructure. It presents the history of matter science and the establishment of metallography. The chapter provides an overview of the progress of steel technology, progress in synthetic polymers and ceramics, and establishment and development of materials science.

This appendix provides a brief introduction to Thermo-Calc, explains what it is, and lists its uses. Instructions for accessing a demonstration version of the software are also provided.

Phase diagrams serve as a map to the phases present in an alloy at different temperatures and compositions. They also help in assessing mechanical properties, selecting heat treat temperatures, warning of possible solidification problems, and identifying routes for creating desired microstructures. This chapter familiarizes readers with the information contained in binary phase diagrams and the methods used to extract it. It explains how thermocouple measurements are used to determine liquidus, solidus, and eutectic reaction lines, how differential scanning calorimetry shows where phase reactions occur, and how x-ray diffraction identifies the actual phases present. It demonstrates the use of tie lines for determining phase composition at different temperatures and the application of the level rule to calculate phase fractions. It also discusses the CALPHAD method and presents computed binary phase diagrams that account for the presence of inclusions, oxygen content, and secondary phases.

This appendix lists the intermetallic phase designations of aluminum-silicon casting alloys and defines symbols and abbreviations associated with the variables, processes, and tools used in microstructural examination.

This chapter focuses on stress-corrosion cracking (SCC) of metals and their alloys. It is intended to familiarize the reader with the phenomenological and mechanistic aspects of stress corrosion. The phenomenological description of crack initiation and propagation describes well-established experimental evidence and observations of stress corrosion, while the discussions on mechanisms describe the physical process involved in crack initiation and propagation. Several parameters that are known to influence the rate of crack growth in aqueous solutions are presented, along with important fracture features.