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.

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.

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 describes the basics of energy and entropy and “free energy.” Fundamentals of internal energy U , the enthalpy H , entropy S , free energies G , and F of a substance are presented. The chapter also presents the thermal vibration model to promote a better understanding of the U , S , and F of the crystal. It covers basic concepts of thermodynamics of magnetic transition and discusses the role and the meaning of magnetic transition in iron and steel. The chapter concludes with a general discussion on an amorphous phase from a thermodynamic viewpoint.

This chapter explains the idea of solution theory and the nature of mixed materials. The chapter considers approximation of free energy by the regular solution model and sublattice model. It discusses chemical potential and nonrandom distribution based on the interactions between solute atoms.

This chapter provides a short introduction to phase transformations, namely, the liquid-to-solid phase transformations that occur during solidification and the solid-to-solid transformations that are important in processing, such as heat treatment. It also introduces the concept of free energy that governs whether or not a phase transformation is possible, and then the kinetic considerations that determine the rate at which transformations take place. The chapter also describes important solid-state transformations such as spinodal decomposition and martensitic transformation.

Phase diagrams are graphical representations that show the phases present in the material at various compositions, temperatures, and pressures. This chapter begins with a section describing the construction of phase diagrams for the simple binary isomorphous system. A binary phase diagram can be used to determine three important types of information: the phases that are present, the composition of the phases, and the percentages or fractions of the phases. The chapter then describes the construction of one common type of binary phase diagram i.e., the eutectic alloy system. The major eutectic systems include the aluminum-silicon eutectic system and the lead-tin eutectic system. The chapter discusses the construction of eutectic phase diagrams from free energy curves. It also provides information on peritectic, monotectic, and solid-state reactions in alloy systems. The presence of intermediate phases is also described. Finally, a brief section provides some information on ternary phase diagrams.

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 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.