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.

A working knowledge of diffusion is necessary to understand and predict the behavior of metals and alloys during manufacturing and in certain types of service. This chapter covers the fundamentals of diffusion in solids and some of the applications in which diffusion plays a role. It discusses the mechanisms behind interstitial, substitutional, grain boundary, and surface diffusion, the derivation and use of Fick’s laws, and the basic principles of diffusion coating processes, including carburizing, nitriding, nitrocarburizing, cyaniding, carbonitriding, boriding, aluminizing, siliconizing, chromizing, vanadizing, and titanizing. It also discusses diffusion bonding and presents several approaches for dealing with oxide barrier problems.

When a metal is alloyed with another metal, either substitutional or interstitial solid solutions are usually formed. This chapter discusses the general characteristics of these solutions and the effects of several alloying elements on the yield strength of pure metals. It presents four rules that give a qualitative estimate of the ability of two metals to form substitutional solid solutions: relative size factor, chemical affinity factor, relative valency factor, and lattice type factor. The chapter provides information on alloys that form an ordered structure during heating. It describes the intermediate phases that are formed during solidification between the two extremes of substitutional solid solution on the one hand and intermetallic compound on the other. The chapter concludes with a section on strain aging in low-carbon steels that allows the interstitial atoms to diffuse to the dislocations and again form atmospheres that pin dislocation movement.

Metallurgy, as discussed in this chapter, focuses on phases normally encountered in stainless steels and their characteristics. This chapter describes the thermodynamics and the three basic phases of stainless steels: ferrite, austenite, and martensite. Formation of the principal intermetallic phases is also covered. In addition, the chapter provides information on carbides, nitrides, precipitation hardening, and inclusions.

This chapter discusses the characteristics of eutectoid transformations, a type of solid-state transformation associated with invariant reactions, focusing on the iron-carbon system of steel. It describes the compositions, characteristics, and properties of ferrite, eutectoid, hypoeutectoid, and hypereutectoid structures and how they are affected by the addition of various alloying elements. The chapter also discusses the formation of peritectoid structures in the uranium-silicon alloy system.

This chapter discusses the alloy composition, metallurgy, mechanical behavior, stabilization, texture, anisotropy, high-temperature properties, and corrosion and oxidation resistance of ferritic stainless steels.

This chapter familiarizes readers with the use of Fick’s laws of diffusion in heat treating, coating, and other metallurgical processes. It contains worked solutions to nearly 30 problems requiring the calculation of activation energy, diffusion coefficient, concentration level, surface layer thickness, case depth, and processing time and temperature. The selected problems deal with various types of iron, steel, and nonferrous alloys and processes ranging from aluminizing, chromizing, carburizing, and plasma nitriding to hydrogen dissipation, decarburizing, and oxidation. A few diffusion problems involving single-crystal silicon are also included.

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.

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 examines the isothermal phase transformations of the iron-carbide system. The discussion includes the formation of ferritic, eutectoid, hypoeutectoid, hypereutectoid, bainitic, and martensitic microstructures as well as their properties, composition, and metallurgy. The use of time-temperature-transformation (TTT) diagrams in understanding the phase transformations and the changes in the isothermal transformation curves due to the addition of carbon and other alloying elements are also discussed.

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.

The existence of austenite and ferrite, along with carbon alloying, is fundamental in the heat treatment of steel. In view of the importance of structure and its formation to heat treatment, this chapter describes the various microstructures that form in steels, the various factors that determine the formation of microstructures during heat treatment processing of steel, and some of the characteristic properties of each of the microstructures. The discussion also covers the constitution of iron during heat treatment and the phases of heat-treated steel with elaborated information on iron phase transformation, hysteresis in heating and cooling, ferrite and austenite as two crystal structures of solid iron, and the diffusion coefficient of carbon.

This chapter briefly reviews the history of brazing from ancient times to the early 20th century.