This chapter describes the structures, phases, and phase transformations observed in metals and alloys as they solidify and cool to lower temperatures. It begins with a review of the solidification process, covering nucleation, grain growth, and the factors that influence grain morphology. It then discusses the concept of solid solutions, the difference between substitutional and interstitial solid solubility, the effect of alloying elements, and the development of intermetallic phases. The chapter also covers the construction and use of binary and ternary phase diagrams and describes the helpful information they contain.

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 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 construction, interpretation, and use of ternary phase diagrams. It begins by examining a hypothetical phase space diagram and several corresponding two-dimensional plots. It then describes one of the most basic tools of metallurgy, the Gibbs triangle, and explains how to construct tie lines to analyze intermediate compositions and phases. It also discusses the use of three-dimensional temperature-composition diagrams, three- and four-phase equilibrium phase diagrams, and binary and ternary phase diagrams associated with the iron-chromium-nickel alloy system.

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 is a compilation of beryllium phase diagrams, representing more than 25 binary alloy systems from beryllium-aluminum to beryllium-zirconium. Each diagram is presented along with a summary and source reference.

This chapter explains the significance of the phase diagram and its use in the development of new materials. The chapter describes the basic rules of heterogeneous equilibrium, presents a comparison between liquidus line and solidus line, and provides information on the solubility curve and the binodal curve.

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.

In order to understand how the strength of steels is controlled, it is extremely useful to have an elementary understanding of two topics: solutions and phase diagrams. This chapter provides an introduction to these topics with suitable examples.

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.

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 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 chapter discusses the use of phase diagrams in alloy design, processing, and performance assessment. The examples cover both ferrous and nonferrous metals and a variety of goals and objectives. The chapter also identifies limitations and pitfalls associated with the use of phase diagrams.

This appendix contains sample problems with worked solutions pertaining to the use of binary phase diagrams. The problems require the determination of favorable temperatures and compositions, the amount and composition of phases in an alloy at a given temperature, the amount of a certain phase in different steels, and the microstructure developed in different alloys.

Steel is made by adding carbon to iron, producing a solid solution defined by its crystalline structure. This chapter discusses the effect of carbon composition and temperature on the types of structures, or phases, that form. Using detailed phase diagrams, it explains how low-carbon (hypoeutectoid) and high-carbon (hypereutectoid) steels are made, how they are classified, and how they compare. It also describes eutectoid steels which, at 0.77 wt% C, form a separate class noted for its microstructure.

This appendix includes two annotated iron-carbon (Fe-C) phase diagrams. One is a poster-size diagram showing iron-carbon phases up to 7 wt% C along with representative microstructures. The other diagram is close-up view showing the phases that occur from 0 to 1.2 wt% C. It also includes labels identifying the microconstituents that form in plain carbon steels under rapid quenching conditions.