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.

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 covers regulatory requirements, safe handling practices, hazard analysis and control, dismantling and decommissioning, and waste disposal. It also includes references for additional information on government regulations.

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 introduces many of the key concepts on which metallurgy is based. It begins with an overview of the atomic nature of matter and the forces that link atoms together in crystal lattice structures. It discusses the types of imperfections (or defects) that occur in the crystal structure of metals and their role in mechanical deformation, annealing, precipitation, and diffusion. It describes the concept of solid solutions and the effect of temperature on solubility and phase transformations. The chapter also discusses the formation of solidification structures, the use of equilibrium phase diagrams, the role of enthalpy and Gibb’s free energy in chemical reactions, and a method for determining phase compositions along the solidus and liquidus lines.

This chapter provides a brief overview of phase diagrams, explaining what they represent and how and why they are used. It identifies key points, lines, and features on a binary nickel-copper phase diagram and explains what they mean from a practical perspective. It also discusses the concept of equilibrium, the significance of Gibb’s phase rule, the theorem of Le Chatelier, and the use of the lever rule.

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 describes the physical characteristics, properties, and behaviors of solid solutions under equilibrium conditions. It begins with a review of a single-component pure metal system and its unary phase diagram. It then examines the solid solution formed by copper and nickel atoms. It discusses the difference between interstitial and substitutional solid solutions and the factors that determine the type of solution that two metals are likely to form. It also addresses the development of intermediate phases, the role of free energy, transformation kinetics, liquid-to-solid and solid-state phase transformations, and the allotropic nature of metals.

This chapter describes surface modification processes that go beyond conventional heat treatments, including plasma nitriding, plasma carburizing, low-pressure carburizing, ion implantation, physical and chemical vapor deposition, salt bath coating, and transformation hardening via high-energy laser and electron beams. The chapter compares methods and includes several example applications.

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 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.

This chapter discusses some of the methods and measurements used to construct phase diagrams. It explains how cooling curves were widely used to determine phase boundaries, and how equilibrated alloys examined under controlled heating and cooling provide information for constructing isothermal and vertical sections as well as liquid projections. It also explains how diffusion couples provide a window into local equilibria and identifies typical phase diagram construction errors along with problems stemming from phase-boundary curvatures and congruent transformations.

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.

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.

Diffusion is the movement of atoms through the crystalline lattice. This chapter discusses the two main types of diffusion that can occur in solids: interstitial diffusion and substitutional diffusion. It describes Fick's first and second laws of diffusion, with emphasis on several applications of the latter. The chapter also provides information on the temperature dependence of diffusion, intrinsic diffusion coefficients (Kirkendall effect), and high diffusion paths.

This chapter discusses the basic principles of precipitation hardening, an important strengthening mechanism in nonferrous alloys as well as stainless steel. It begins with a detailed review of the theory of precipitation hardening, then describes its application to aluminum alloys and nickel-base superalloys.

The building block of all matter, including metals, is the atom. This chapter initially provides information on atomic bonding and the crystal structure of metals and alloys, followed by a description of three crystal lattice structures of metals: face-centered cubic, hexagonal close-packed, and body-centered cubic. It then describes the four main divisions of crystal defects, namely point defects, line defects, planar defects, and volume defects. The chapter provides information on grain boundaries of metals, processes involved in atomic diffusion, and key properties of a solid solution. It also explains the aspects of a phase diagram that shows what phase or phases are present in the alloy under conditions of thermal equilibrium. Finally, a discussion on the applications of equilibrium phase diagrams is presented.

Stainless steel retains strength and has excellent oxidation resistance from room temperature to nearly 1000 deg C relative to competitive materials. This chapter focuses on the high-temperature oxidation of stainless steel by oxygen or water vapor. It begins by discussing the thermodynamic conditions and electrochemical nature of oxidation and providing information on transient oxidation. This is followed by a description of Wagner's theory for metal oxidation. The volatile nature of Cr 2 O 3 is then reviewed. The chapter further discusses the causes and preventive measures of spalling and cracking of oxide scale. It ends with a section providing information on oxidation behaviors under less-oxidizing atmospheres.