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 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.

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 discusses the corrosion behavior of titanium, the types of corrosion that can occur, and the effect of alloying on corrosion resistance. It explains that, due to its tenacious oxide film, titanium has excellent corrosion resistance in oxidizing environments and that the resistance can be extended into the “reducing-acid” region by adding a small amount of palladium. It describes how different grades of titanium respond to different forms of attack, including uniform, crevice, and galvanic corrosion. It also identifies applications where corrosion is often a concern.

Corrosion involves chemical reactions in equilibrium that that are understood through principles of thermodynamics. In practice, the rate at which corrosion reactions occur is the most important consideration. This chapter deals with corrosion kinetics, which allows engineers to to understand rates of corrosion. The discussion covers two kinetic processes, namely electrode reactions at the cathode and anode and conduction of ions in the electrolyte. The chapter also provides information on passivation and its effect on polarization diagrams.

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.

This chapter explores the behavior of stainless steel in media that promote corrosion. The forms of corrosion covered are uniform corrosion, atmospheric corrosion, localized corrosion, pitting corrosion, crevice corrosion, and grain boundary corrosion. The chapter discusses the influence of material and environmental variables on stress-corrosion cracking (SCC) and the mechanisms proposed for SCC in stainless steel, comparing the mechanism of SCC with hydrogen embrittlement. In addition, it provides information on biocorrosion and microbiologically induced corrosion in ambient aqueous environments.

In the second step of the four-step problem-solving process, the failure analysis team should identify all potential failure causes. This chapter discusses the steps involved in five such techniques for identifying potential causes of failure, namely brainstorming, mind mapping, Ishikawa diagrams, the “five whys” technique, and flow charting.

This chapter explains how polymeric adhesives are applied to composite as well as metal parts, forming bonded structures. It describes surface preparation practices and techniques, epoxy selection and use, and bonding procedures.

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 a detailed account of cathodic protection. It begins by discussing the fundamentals of cathodic protection followed by a description of the various types of cathodic protection. It then describes the origins, types, and alleged failures of cathodic protection criteria. This is followed by a section providing information on anode materials that are used for cathodic protection applications. General guidelines for designing the cathodic protection systems are also listed. Finally, the chapter presents various examples on cathodic protection of steel structures. The examples are selected to familiarize the design engineer with the steps to follow in selecting a specific corrosion-control method.

This chapter provides an overview of the tools and techniques, as well as some of the underlying theory, that have proven useful for process modeling and simulation. It begins by presenting the framework of a thermoset cure model that accounts for kinetics, viscosity, heat transfer, flow, voids, and residual stress. It then discusses each variable in detail, explaining how it affects the cure process, how it is measured, and how it can be expressed mathematically in the form of a simple model. The discussions throughout the chapter are supported by numerous images, diagrams, and data plots.

Statistics, data analysis, root cause analysis, and problem-solving processes play a key role in failure investigations. This chapter explains how to collect failure investigation data, how to build and maintain a database for company-related failures, and how to use corresponding statistics including type of failure, material, and root cause. It describes the purpose and benefits of conducting a root cause analysis and the factors, namely relative failure importance and company value, that determine when an investigation should be performed. The chapter also discusses the four-step problem-solving process as it applies to failure investigation, how to assemble an investigation team, and the details of organization and planning. It concludes with a case history of the Firestone 500 steel-belted tire failure, stressing the importance of a systematic approach to failure investigations.

This chapter concentrates on the better-known and widely studied phenomenon of pitting corrosion of passive metals. The discussion focuses on different parameters that influence pitting corrosion, namely environment, metal composition, potential, temperature, surface condition, and inhibitors. It also provides information on various stages of pitting: passive film breakdown, metastable pitting, pit growth, and pit stifling or death.

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.

Adhesive bonding is a widely used industrial joining process in which a polymeric material is used to join two separate pieces (the adherends or substrates). This chapter begins with a discussion on the advantages and disadvantages of adhesive bonding, followed by a section providing information on the theory of adhesion. The chapter then describes the considerations for designing adhesively bonded joints and for testing or characterizing adhesive materials. The following section covers the characteristics of the most important synthetic adhesive systems and five groups of adhesives, namely structural, hot melt, pressure sensitive, water based, and ultraviolet and electron beam cured. The chapter ends with a discussion on some general guidelines for adhesive bonding and the basic steps in the adhesive bonding process.

High-strength steels are susceptible to stress-corrosion cracking (SCC) even in moist air. This chapter identifies such steels and the applications where they are typically found. It provides information on crack growth kinetics and crack propagation models in which hydrogen embrittlement is the predominant mechanism. It explains how different application variables affect SCC, including loading mode, state of stress, type of steel, temperature, electrochemical potential, heat treatment, and deformation processes. It also compares SCC characteristics in different high-strength steels and discusses the influence of composition, steelmaking practice, and application environment.

This article describes in detail the process of corrosion control by cathodic and anodic protection. The discussion covers the basic concept of cathodic and anodic protection systems, their types and equipment used, and the advantages, limitations, and applications of these protection systems. The types of cathodic protection systems include sacrificial cathodic protection and impressed-current cathodic protection systems. Some of the technical problems associated with cathodic protection include the effects of stray currents on the corrosion of adjacent metal structures, the effects of the chemical reactions occurring at the surface of the protected structure, and the effects of cathodic protection on coatings.

Aluminum is protected by a barrier oxide film that, if damaged, reforms immediately in most environments. Despite this inherent corrosion resistance, there are conditions where aluminum alloys, like many materials, are subject to the effects of stress-corrosion cracking (SCC). This chapter describes those conditions, focusing initially on the effects of alloying elements and temper on solution potential and how it compares to other metals. It then addresses the issue of intergranular corrosion and its role in SCC. It explains how factors such as stress loads, grain structure, and environment determine whether or not stress-corrosion cracking develops in a susceptible alloy. It also provides stress-corrosion ratings for many alloys, tempers, and product forms and includes information on hydrogen-induced cracking.

This chapter presents a step-by-step approach for analyzing the causes of nonconforming workpieces and determining potential solutions. The discussion covers a wide range of issues, including testing errors, latent and process-related defects, examination and testing techniques, defect characterization, and effective remedial actions.