This chapter discusses the metallurgical considerations and process requirements of nitriding. It presents the pioneering work of Adolph Machlet and Adolph Fry and presents early developments. One such development is the Floe process, a two-stage treatment used to reduce the formation of a compound layer on the surface of a nitrided steel.

The unique advantages of the nitriding process were recognized by German researchers in the early 1920s. It was used to treat steels for applications that required: high torque, high wear resistance; abrasive wear resistance; corrosion resistance; and high surface compressive strength. This chapter focuses on key process considerations and factors that helped nitriding gain acceptance. These factors include a low-temperature process, no quench requirement, minimal distortion, high hardness values, and resistance to oxidation.

Several process parameters must be considered to ensure success in achieving desired metallurgical properties and to minimize distortion. This chapter provides a detailed discussion on the liberation of nitrogen, dissociation of the gas at the selected nitriding temperature, why ammonia is used, distortion, and preheat treatment.

Formation of the nitrided case begins through a series of nucleated growth areas on the steel surface. These nucleating growth areas will eventually become what is known as the compound layer or, more commonly, the white layer. This chapter discusses the influence of carbon on the compound zone. It explains how to control and calculate compound zone thickness. Compound zone thickness can be controlled by dilution, the two-stage Floe process, or by ion nitriding. The chapter describes the factors affecting surface case formation.

This chapter provides a discussion of nitriding furnace equipment and control systems. The discussion covers the essential design criteria of the furnace, types of nitriding furnaces, insulation for the reduction of furnace heat losses, and factors influencing furnace configuration and design. It also covers the processes involved in the construction and maintenance of retorts, methods for sealing a retort to prevent ammonia leaks, and safety precautions to be taken while using ammonia. Further, the chapter provides information on the factors for choosing a heating medium and discusses the processes involved in controlling temperature, gas dissociation, oxygen probes, and nitriding sensors.

This chapter presents the salts used and the process advantages of salt bath nitriding. It describes bath testing and analysis including the materials and equipment, analysis procedure, and determination of sodium carbonate and sodium cyanate for titration testing of the nitriding salt bath. The chapter explains the procedures for maintenance of the salt bath and related equipment. It also discusses safety precautions and design parameters for furnace equipment.

The compound zone that forms on the surface of nitrided steels is often called the white layer. When the nitrided sample is sectioned through the case, and then polished and etched with a standard solution of nital (2 to 5% nitric acid and alcohol), the immediate surface etches out as white in appearance above the nitrided case. This chapter focuses on the methods to control the compound zone, or white layer. It first provides information on a test to determine the presence of the white layer, and discusses the processes involved in the reduction of the compound zone by the two-stage process. Next, it describes other methods for controlling compound zone formation, and, finally, reviews the factors related to the determination of case depth in nitriding.

This chapter begins with an overview of the history of ion nitriding. This is followed by sections that describe how the ion nitriding process works, glow discharge characteristics, process parameters requiring good control, and the applications of plasma processing. The chapter explores what happens in the ion nitriding process and provides information on its gas ratios. It describes the reactions that occur at the surface of the material being treated during iron nitriding and defines corner effect and nitride networking. Further, the chapter provides information on the stability of surface layers and processes involved in the degradation of surface finish and control of the compound zone formation. Gases primarily used for ion nitriding and the control parameters used in ion nitriding are also covered. The chapter also presents the philosophies and advantages of the plasma generation technique for nitriding. It concludes with processes involved in oxynitriding.

Ion nitriding equipment can be categorized into two groups: cold-wall continuous direct current (dc) equipment and hot-wall pulsed dc equipment. This chapter focuses on these two categories along with other important considerations for ion (plasma) nitriding equipment and processing. Other important considerations discussed include the hollow cathode effect, sputter cleaning, furnace loading, pressure/voltage relationships, workpiece masking, and furnace configuration options. The chapter describes five methods of cooling parts from the process temperature to an acceptable exposure temperature after plasma nitriding. The chapter also presents some of the advantages of the pulsed plasma process.

A fluidized-bed furnace system can be used for the gas nitriding process. This chapter focuses on fluidized-bed nitriding. It discusses the methods of heating a fluidized bed. The heating system can be electrical or gas, and internal or external. The chapter describes nitriding and oxynitriding processes in the fluidized-bed furnace. It also explains how to operate the fluid bed for nitriding. The chapter provides a discussion on the measurement of the gas dissociation.

Distortion is defined as an irreversible and usually unpredictable dimensional change in a component due to thermal processing or temperature variations and loading in service. This chapter describes two types of distortion: size distortion and shape distortion. It addresses how distortion can be managed by controlling certain factors. The chapter discusses the cause and effect of distortion during nitriding, the processes involved in stock removal prior to nitriding, and the criteria for post-machining operations.

This chapter first lists the compositions of typical steels that are suitable for nitriding. It then presents considerations for steel selection. The chapter also shows the influence of alloying elements on hardness after nitriding and the depth of nitriding. It provides a detailed discussion on plasma nitriding of type 422 stainless steel, nitriding of type 440A and type 630 (17-4 PH) stainless steel. The chapter also discusses plasma nitride case depths.

Process gas control for plasma (ion) nitriding is a matter of estimating the flows necessary to accomplish the required surface metallurgy. This chapter reviews several studies aimed at better understanding process gas control in plasma nitriding and its influence on compound zone formation. Emphasis is placed on the effect of sputtering on the kinetics of compound zone formation. The discussion covers the processes involved in process gas control analysis by photo spectrometry and mass spectrometry and the difficulties associated with gas analysis.

The nitriding process can be applied to various materials and part geometries. This chapter focuses on tool steels, pure irons, low-alloy steels, and maraging steels. Various considerations such as the surface metallurgy requirements of the die, including case depth, compound layer formation, and temperature, are also discussed in this chapter. The chapter also addresses steel selection and surface metallurgy of gears.

Stop-off coatings prevent nitriding of selected areas on components. This chapter discusses the processes, advantages, and disadvantages of stop-off techniques for gas nitriding, salt bath nitriding, and ion nitriding.

Examining and evaluating the nitrided case is generally accomplished by hardness testing and microscopic examination. This chapter discusses both characterization methods, as well as sample preparation. The chapter also discusses the processes involved in the etching of the sample after microhardness testing and provides practices that contribute to the safe preparation of specimens. Examples of nitrided case microstructures, using optical light microscopy, are also presented.

This chapters reviews the various process, material, and post-treatment problems that can occur in nitriding and how to troubleshoot them. The troubleshooting methods discussed relate to gas nitriding, salt bath nitriding, and ion nitriding.

Ferritic nitrocarburizing accomplishes surface treatment of a part in the ferrite region of the iron-carbon equilibrium diagram. This chapter presents the history and process benefits of ferritic nitrocarburizing.

This chapter provides a detailed discussion of salt bath nitrocarburizing. Process variations discussed include low-cyanide salt bath ferritic nitrocarburizing, salt bath nitrocarburizing plus post treatment, and the Kolene Nu-Tride process.

Gaseous ferritic nitrocarburizing, like salt bath nitrocarburizing, involves the introduction of carbon and nitrogen into steel in order to produce a thin layer of iron carbonitride and nitrides, the "white layer" or compound layer, with an underlying diffusion zone containing dissolved nitrogen and iron (or alloy) nitrides. This chapter first presents the development and principles of the process. It then discusses the properties of gaseous ferritic nitrocarburized components. The chapter also presents the applications for the ferritic nitrocarburizing process. It provides an overview of the safety considerations.