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 explains how the presence of intermediate phases affects the melting behavior of binary alloys and the transformations that occur under different rates of cooling. It begins by examining the phase diagrams of magnesium-lead and copper-zinc, noting some of the complexities associated with intermediate phases. It then discusses the difference between ordered and disordered phases and how they are accounted for on phase diagrams. It describes how the atoms in a disordered solution may arrange themselves into an ordered array, forming a superlattice in the process of cooling, and goes on to identify the most common superlattice structures and their corresponding alloy phases. It also discusses the factors that limit the formation of superlattices along with the kinetics of spinodal decomposition and its effect on microstructure development.

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 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 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 appendix provides a detailed overview of the crystal structure of metals. It describes primary bonding mechanisms, space lattices and crystal systems, unit cell parameters, slip systems, and crystallographic planes and directions as well as plastic deformation mechanisms, crystalline imperfections, and the formation of surface or planar defects. It also discusses the use of X-ray diffraction for determining crystal structure.

This chapter examines two important strengthening mechanisms, martensitic and bainitic transformations, both of which occur under nonequilibrium cooling conditions. It explains how time-temperature-transformation diagrams are constructed and how they are used to understand and control the formation of martensite and bainite in steel and other alloys. It describes the morphology of both types of structures, the factors that influence their formation, how they respond to tempering processes, and their effect on mechanical properties and behaviors. It also discusses the role of transformation hysteresis in shape memory alloys.

This chapter focuses on the applications of stainless steels in chemical and process industry, covering what data are necessary and how they can be found. It begins with an overview of single- and dual-environment systems and the corrosion issues they face. This is followed by a discussion on the causes of the various forms of corrosion associated with liquids, namely pitting corrosion, crevice corrosion, intergranular corrosion, stress corrosion cracking, and erosion corrosion. The chapter also contains tables listing corrosion rates of sulfuric acid and fuming sulfuric acid. It ends with a section providing information on specific environments against which stainless steels are resistant to select for use in the chemical process industries.

The overall chemical composition of metals and alloys is most commonly determined by x-ray fluorescence (XRF) and optical emission spectroscopy (OES). High-temperature combustion and inert gas fusion methods are typically used to analyze dissolved gases (oxygen, nitrogen, and hydrogen) and, in some cases, carbon and sulfur in metals. This chapter discusses the operating principles of XRF, OES, combustion and inert gas fusion analysis, surface analysis, and scanning auger microprobe analysis. The details of equipment set-up used for chemical composition analysis as well as the capabilities of related techniques of these methods are also covered.

This chapter familiarizes readers with the machining characteristics of titanium and the implementation of machining and shaping processes. It explains why titanium alloys are more difficult to machine than other metals and how it impacts the equipment and procedures that can be used. It describes the basic machining requirements for titanium in terms of tool geometry and materials, machine setup rigidity, cutting speeds and feed rates, and surface conditions, and explains how the requirements are met in practice in milling, turning, drilling, surface grinding, and broaching operations. The chapter also covers chemical and electrochemical machining processes as well as flame cutting.

This article discusses the chemical susceptibility of a polymeric material. The discussion covers significant absorption and transportation of an environmental reagent by the polymer; the chemical susceptibility of additives; and thermal degradation, thermal oxidative degradation, photo-oxidative degradation, environmental corrosion, and chemical corrosion of polymers. It also includes some of the techniques used to detect changes in structure during polymer exposure to hostile environments. In addition, the article describes the effects of environment on polymer performance, namely plasticization, solvation, swelling, environmental stress cracking, polymer degradation, surface embrittlement, and temperature effects.

This article focuses on characterization techniques used for analyzing the physical behavior and chemical composition of thermoset resins, namely chromatography and infrared spectroscopy. The main purpose is to give sufficient detail to permit the reader understand a particular test technique and its value to the thermoset resin field. Epoxy resins are emphasized in the examples because they dominate the airframe and aerospace industries. The article also provides information on two categories of characterization of the processing behavior of thermoset. The first studies the thermal properties of reactive thermoset systems, while the second utilizes these thermal characteristics as the basis for monitoring and control during processing.

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.

This chapter provides an overview of the state of the art in high-pressure cold spray equipment, including both spray systems and gas supply systems. The chapter describes the commercial cold spray systems developed by companies such as Cold Gas Technology (CGT) GmbH, Plasma Giken Company Ltd, Impact Innovations GmbH, and ASB Industries. Typical helium and nitrogen gas systems used in high-pressure cold spray processing are reviewed.

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 develops a corrosion model that accounts for solution potentials and the effects of coupling between cathodic and anodic reactions. It begins by examining potential differences at various points (in the solution) along a path from the anode to the cathode area. It then presents a simple model of a galvanically coupled electrode, in which the metal is represented as an array of anode and cathode reaction surfaces. The chapter goes on to develop the related theory of mixed electrodes, showing how it can be used to predict corrosion rates based on measured potentials and current densities, polarization characteristics, and physical variables such as anode-to-cathode area ratios and fluid velocity. It also discusses the effect of corrosion inhibitors, galvanic coupling, and external currents, making extensive use of polarization curves.

Irradiation-assisted stress-corrosion cracking (IASCC) has been a topic of engineering interest since it was first reported in the 1960s, having been observed in stainless steel cladding on light water reactor fuel elements. This chapter summarizes the results of decades of investigation, showing that IASCC can essentially be defined as the intergranular cracking of austenitic alloys in high-temperature water, where both the material and its environment have been altered by radiation. Of the many interactions that can occur when metals and water are exposed to radiation, the international consensus is that the three with the greatest impact on crack growth rates are the formation of material defects, radiation-induced segregation, and chemical reactions that increase the corrosion potential of water. The chapter discusses each of these in great detail, and includes information on predictive modeling as well.

After the fault-tree, a failure-cause identification method has identified potential failure causes and the failure analysis team has prepared a failure mode assessment and assignment (FMA&A). The team knows specifically what to search for when examining components and subassemblies from the failed system. There are numerous techniques and technologies available for examining and analyzing components and subassemblies, which are categorized as follows: optical approaches, dimensional inspection and related approaches, nondestructive test approaches, mechanical and environmental approaches, and chemical and composition analysis for assessing material characteristics. This chapter is a detailed account of the working principle and the steps involved in these techniques and technologies.