Sulfur is one of the most common corrosive contaminants in high-temperature industrial environments and its presence can cause a number of problems, including sulfidation. This chapter describes the sulfidation behavior of a wide range of alloys as observed in three types of industrial environments. One environment consists of sulfur vapor, hydrocarbon streams, H2S, and H2-H2S gas; sulfides are the only corrosion products that form under these conditions. Another environment consists of H2, CO, CO2, H2S, and other gases, causing the formation of oxides as well as sulfides in most alloys. The third environment, for which less data exists, contains either SO2 or O2-SO2 mixtures.

Nickel and nickel-base alloys are specified for many applications, such as oil and gas production, power generation, and chemical processing, because of their resistance to stress-corrosion cracking (SCC). Under certain conditions, however, SCC can be a concern. This chapter describes the types of environments and stress loads where nickel-base alloys are most susceptible to SCC. It begins with a review of the physical metallurgy of nickel alloys, focusing on the role of carbides and intermetallic phases. It then explains how SCC occurs in the presence of halides (such as chlorides, bromides, iodides, and fluorides), sulfur-bearing compounds (such as H2S and sulfur-oxyanions), high-temperature and supercritical water, and caustics (such as NaOH), while accounting for temperature, composition, microstructure, properties, environmental contaminants, and other factors. The chapter also discusses the effects of hydrogen embrittlement and provides information on test methods.

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.

This chapter discusses the conditions under which carburization and metal dusting occur. It describes the chemical reactions and thermodynamic relationships that drive carburization and metal dusting attack and the factors that determine the amount of damage that metals and alloys are likely to sustain. The chapter also explains how carburization affects creep strength and fracture toughness, and how surface conditions and finish and the presence of sulfur affect metal dusting behaviors.

This chapter addresses the issue of stress-corrosion cracking (SCC) in carbon and low-alloy steels. It discusses crack initiation, propagation, and fracture in aqueous chloride, hydrogen sulfide, sulfuric acid, hydroxide, ammonia, nitrate, ethanol, methanol, and hydrogen gas environments. It explains how composition and microstructure influence SCC, as do mechanical properties such as strength and fracture toughness and processes such as welding and cold work. It also discusses the role of materials selection and best practices for welding.

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.

The properties of cast iron are determined primarily by the form of carbon they contain, which in turn, is controlled by modifying compositions and cooling rates during casting. Certain alloys (such as Si, Al, Ni, Co, and Cu) promote graphite formation, while others (such as S, V, Cr, Sn, Mo, and Mn) promote the formation of cementite. This chapter examines the relative potencies of these alloys and their effect on microstructure. It covers the five most common commercial cast irons, including white, gray, ductile, malleable, and compacted graphite, describing their compositional ranges, distinguishing features, advantages, limitations, and applications.

Fossil fuels produce many byproducts that, if not fully combusted, put boiler tubes at risk. Fuel ash, chemical residues, and process heat pose the greatest threat and are the primary contributors to fireside corrosion. This chapter covers various types of fireside corrosion such as waterwall, fuel ash, and hot corrosion, acid dew-point or cold-end corrosion, and polythionic acid corrosion. It also addresses stress corrosion cracking and includes relevant case studies.

This chapter focuses on the metallurgical factors governing the machinability of stainless steels. It begins by describing the chemistry, cleanliness, structure, processing history, and the cross-section size of the stock of the different grades of stainless steel. This is followed by a general description of the machining behavior of the stainless steel families, namely ferritic, martensitic, austenitic, precipitation hardening, duplex, and super stainless steels. The beneficial effect of controlled inclusions is then discussed. The chapter ends with a section providing information on high-speed tool steel and carbide tooling, along with tool coatings and coolants applicable to stainless steel.

This appendix provides corrosion rate values for various grades of commercially pure and alloyed titanium. The values were derived from published sources and in-house laboratory tests. These data serve only as a starting point or initial guideline for corrosion performance.

This chapter discusses the practices and procedures used to reveal and record macrostructural features such as hardening depth, weld thickness, crack size, porosity, hot folds, and machining and tooling marks. It provides information on sectioning, sample location, orientation, surface grinding, and etching. It describes macrographic etchants and the features they reveal along with common etching problems and how to avoid them. It explains how to evaluate etching results and how they can be improved using remedial processes such as light grinding. It also discusses photographic reproduction, lighting, and image enhancement techniques.

Corrosive environments can be broadly classified as atmospheric, underground/soil, water, acidic, alkaline, and combinations of these. Complicating matters is the fact that there are important variables, for example, pH, temperature, and the presence of biological organisms, that can significantly alter the response of the material in a given environment. This chapter provides a detailed account of all these types of corrosion affecting various industries, pointing out the connection between the characteristics of the corrosive environment that control corrosion behavior, the corrosion characteristics of various metals and materials systems, and the subsequent corrosion response.

Anodic protection is used on a smaller scale than other corrosion control techniques due to the fundamental electrochemistry involved. This chapter provides a brief history of the technique, discusses anodic protection use, and compares anodic and cathodic protection. The background and theory of anodic protection are summarized. In addition to briefly describing the various items used for each component of an anodic protection system, the chapter presents design concerns as well as applications of the system. Factors concerning the economic justification of anodic protection are also described.

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.

This chapter describes several macroscopic examination techniques, including macroetching, contact printing, fracturing, and lead exudation. It explains how each method is implemented, why it is used, and what it reveals about manufacturing processes, defects, imperfections, and failure mechanisms.

Steels contain a wide range of elements, including alloys as well as residual processing impurities. This chapter describes the chemical composition of low-alloy AISI steels, which are classified based on the amounts of chromium, molybdenum, and nickel they contain. It explains why manganese is sometimes added to steel and how unintended consequences, such as the development of sulfide stringers, can offset the benefits. It also examines the effect of alloying elements on the iron-carbon phase diagram, particularly their effect on transformation temperatures.

This article discusses the composition and morphology of compacted graphite (CG) iron relative to that of gray and ductile iron. It explains that the graphite in CG iron is intermediate in shape between the spheroidal graphite found in ductile iron and the flake graphite in gray iron, giving it distinct advantages in a number of applications. The article also discusses the role of melt treatment elements and explains how alloying and heat treatment affect tensile strength, hardness, toughness, and ductility.

This article examines the role of alloying in the production and use of nickel and its alloys. It explains how nickel-base alloys are categorized and lists the most common grades along with their compositional ranges and corresponding UNS numbers. It describes the role of nearly 20 alloying elements and how they influence strength, ductility, hardness, and corrosion resistance. It also addresses processing issues, explaining how alloying and intermetallic phases affect forming, welding, and machining operations.

This article discusses the steps in the primary processing of stainless steels: melting, refining, remelting, casting, and hot rolling. It provides information of the major categories of defects in hot rolled stainless steels, namely hot mill defects, inclusion-related defects, and hot ductility-related defects.

This chapter focuses on resistance characteristics and methods of protecting different forms of high-temperature gaseous corrosion, namely high-temperature oxidation, sulfidation, carburization, hydrogen effects, and hot corrosion.