This article introduces the fundamental concepts of chemical thermodynamics and chemical kinetics in describing presolidification phenomena. For metallurgical systems, the most important thermodynamic variables are enthalpy and Gibbs free energy. A qualitative demonstration of the interrelationship between phase diagrams and thermodynamics is presented. The article discusses processes that generally limit the rates of chemical processes. These include nucleation of the product phase and interphase mass transport. The article provides a discussion on the dissolution of alloy with melting point lower than bath temperature and dissolution of alloy that is solid at bath temperatures.

This article discusses selected highlights of thermodynamic relationships during solidification and nucleation kinetics behavior in connection with the basis of nucleation treatments, such as grain refinement and inoculation, to provide a summary of nucleation phenomena during casting. Nucleation during solidification is a thermally activated process involving a fluctuational growth in the sizes of clusters of solids. The article describes nucleation phenomenon such as homogeneous nucleation and heterogeneous nucleation. It discusses various grain refinement models, such as carbide-boride model, free growth model, and constitutional undercooling model. The article concludes with a section on thermal analysis techniques for assessing grain-refining characteristics during master alloy processing.

This article begins with the one-component, or unary, diagram for magnesium. The diagram shows what phases are present as a function of the temperature and pressure. When two metals are mixed in the liquid state to produce a solution, the resulting alloy is called a binary alloy. The article describes the various types of solid solutions such as interstitial solid solutions and substitutional solid solutions. Free energy is important because it determines whether or not a phase transformation is thermodynamically possible. The article discusses the thermodynamics of phase transformations and free energy, as well as kinetics of phase transformations. It concludes with a description of solid-state phase transformations that occur when one or more parent phases, usually on cooling, produces a phase or phases.

This article describes the nitriding methods of titanium alloys such as plasma nitriding and gas nitriding. It focuses on the interaction of titanium alloys, interaction of titanium with nitrogen, and the interaction of titanium with oxygen, carbon, and hydrogen. The article provides information on the wear and fatigue properties and corrosion resistance of nitrided titanium alloys, as well as the effect of nitriding on the biocompatibility of titanium. It also compares plasma-nitrided titanium alloys with alloy steels. It concludes with a short discussion on the effect of nitriding on the surface properties of titanium and two-phase a + ß alloys.

This article describes the vapor-phase growth techniques applied to the epitaxial deposition of semiconductor films and discusses the fundamental processes involved in metal-organic chemical vapor deposition (MOCVD). It reviews the thermodynamics that determine the driving force behind the overall growth process and the kinetics that define the rates at which the various processes occur. The article provides information on the reactor systems and hardware, MOCVD starting materials, engineering considerations that optimize growth, and the growth parameters for a variety of Group III-V, II-VI, and IV semiconductors.

Nanofluids offer a completely different behavior of wetting kinetics and heat-removal characteristics, which are exploited in industrial heat treatment for quenching. This article provides information on the important thermophysical properties of nanofluids, namely, thermal conductivity, viscosity, specific heat, density, and surface tension. It reviews wetting and boiling heat-transfer characteristics of nanofluids as quenchants and highlights the importance of using nanofluids as effective quench media for the hardening process during heat treatment. The article describes the effect of nanoparticle addition on the microstructure, mechanical properties of components, wetting kinetics, and kinematics.

Recrystallization is to a large extent responsible for their final mechanical properties. This article commences with a discussion on static recrystallization (SRX) and dynamic recrystallization (DRX). The DRX includes continuous dynamic recrystallization (CDRX) and discontinuous dynamic recrystallization (DDRX). The article discusses the assumptions and simplifications for the Avrami analysis. It describes the effects of nucleation and growth rates on recrystallization kinetics and recrystallized grain size based on the Johnson-Mehl-Avrami-Kolmogorov model for static recrystallization. The article reviews the kinetics of DRX with the aid of the Avrami relations. It considers the basic framework of the mesoscale approach for DDRX, including the three basic equations for grain size changes, strain hardening and dynamic recovery, and nucleation. The article explains the mesoscale approach for CDRX to predict microstructural evolutions occurring during hot deformation, along with an illustration of the main features of the CDRX mesoscale model.

This article discusses the fundamental aspects of phase-field microstructure modeling. It describes the evolution of microstructure modeling, including nucleation, growth, and coarsening. The article reviews two approaches used in the modeling nucleation of microstructure: the Langevin force approach and explicit nucleation algorithm. Calculation of activation energy and critical nucleus configuration is discussed. The article presents the deterministic phase-field kinetic equations for modeling growth and coarsening of microstructure. It also describes the material-specific model inputs, chemical free energy and kinetic coefficients, for phase-field microstructure modeling. The article provides four examples that illustrate some aspects of phase-field modeling.

This article focuses on transport phenomena and modeling approaches that are specific to vapor-phase processes (VPP). It discusses the VPP for the synthesis of materials. The article reviews the basic notions of molecular collisions and gas flows, and presents transport equations. It describes the modeling of vapor-surface interactions and kinetics of hetereogeneous processes as well as the modeling and kinetics of homogenous reactions in chemical vapor deposition (CVD). The article provides information on the various stages of developing models for numerical simulation of the transport phenomena in continuous media and transition regime flows of VPP. It explains the methods used for molecular modeling in computational materials science. The article also presents examples that illustrate multiscale simulations of CVD or PVD processes and examples that focus on sputtering deposition and reactive or ion beam etching.

Hammers and high-energy-rate forging machines are classified as energy-restricted machines as they deform the workpiece by the kinetic energy of the hammer ram. This article provides information on gravity-drop hammers, power-drop hammers, die forger hammers, counterblow hammers, and computer-controlled hammers. It describes the three basic designs of high-energy-rate forging (HERF) machines: the ram and inner frame, two-ram, and controlled energy flow. The article reviews forging mechanical presses, hydraulic presses, drive presses, screw presses, and multiple-ram presses.

The constitutive relations for metalworking include elements of behavior at ambient temperature as well as high-temperature response. This article presents equations for strain hardening and strain-rate-sensitive flow, with alternate sections on empirically determined properties, followed by the models of constitutive behavior. It provides a discussion on creep mechanisms involving dislocation and diffusional flow, such as the Nabarro-Herring creep and the Coble creep. The equations for the several creep rates are also presented. Research on the mechanism of the superplastic flow in fine-grain metals has encompassed many ideas, such as the diffusional creep, dislocation creep with diffusional accommodation at grain boundaries, and concepts of grain-mantle deformation. The article concludes with information on the kinetics of superplastic deformation processes, including low stress behavior, concurrent grain growth, and high stress behavior.

This article discusses the two extremes of solute redistribution that results in microsegregation. The solute redistribution includes equilibrium solidification, nonequilibrium Gulliver-Scheil solidification, and nonequilibrium solidification with back diffusion. The measurement and kinetics of microsegregation are discussed for the binary isomorphous systems: titanium-molybdenum; binary eutectic systems: aluminum-copper and aluminum-silicon; binary peritectic systems: copper-zinc; multicomponent eutectic systems: Al-Si-Cu-Mg; and for systems with both eutectic and peritectic reactions: Fe-C-Cr and nickel-base superalloy.

Rapid solidification is a tool for modifying the microstructure of alloys that are obtained by ordinary casting. This article describes the fundamentals of the four microstructural changes, namely, microsegregation, identity of the primary phase, identity of the secondary phase, and formation of noncrystalline phases. It considers three factors: heat flow, thermodynamic constraints/conditions at the liquid-solid interfaces, and diffusional kinetics/microsegregation, to understand the fundamentals of these changes. These factors are described in detail.

This article begins with balance equations for mass, momentum, energy, and solute and the necessary boundary conditions for solving problems of interest in casting and solidification. The transport phenomena cover a vast range of length and time scales, from atomic dimensions up to macroscopic casting size and from nanoseconds for interface attachment kinetics to hours for casting solidification. The article describes how to determine which phenomena are most important at the particular length and time scale for the problem. It concludes with several examples of the application of transport phenomena in solidification, focusing in particular on microstructure formation.

This article reviews the solubilities of the common gases present in ferrous metals, such as cast irons, and nonferrous metals, such as aluminum, copper, magnesium, and their alloys. The kinetics of the relevant reactions, reactions during solidification, and possible methods of control or removal of the dissolved gases are discussed. The most common method for removing hydrogen from aluminum, copper, and magnesium is inert gas flushing. The article concludes with a discussion on overcoming gas porosity in ferrous and nonferrous metals.

This article, to develop an understanding of the underlying mechanisms governing deformation at elevated temperatures, discusses the phenomenological effects resulting from temperature-induced thermodynamic and kinetic changes. It describes the deformation behavior of engineering materials using expressions known as constitutive equations that relate the dependence of stress, temperature, and microstructure on deformation. The article reviews the characteristics of creep deformation and mechanisms of creep, such as power-law creep, low temperature creep, power-law breakdown, diffusional creep, twinning during creep deformation, and deformation mechanism maps. It discusses the creep-strengthening mechanisms for most structural engineering components. The article provides a description of the microstructural modeling of creep in engineering alloys.

This article describes the results obtained by Volmer, Weber, Farkas, Becker, and Doring, which constitute the classical nucleation theory. These results are the predictions of the precipitate size distribution, steady-state nucleation rate, and incubation time. The article reviews a nucleating system as a homogeneous phase using the classical nucleation theory, along with heterophase fluctuations that led to the formation of precipitates. It discusses the gas cluster dynamics using the kinetic approach to describe nucleation. The article presents key parameters, such as cluster condensation and evaporation rates, to describe the time evolution of the system. The predictions and extensions of the classical nucleation theory are discussed. The article also provides the limitations of classical nucleation theories in cluster dynamics.

The overarching goal of life-prediction research is to develop models for the various types of time dependencies in the crack-tip damage accumulation that occur in materials subjected to elevated temperatures. This article focuses on describing the models based on creep, oxidation kinetics, evolution of crack-tip stress fields due to creep, oxygen ingress, and change in the microstructure. It also provides a summary of creep-fatigue modeling approaches.

This article assesses the evolution of martensite modeling in the changing materials engineering environment. It describes the physics of displacive transformations using Ginzburg-Landau theory, microstructure representation, dynamics and simulations, density functional theory, and shuffle transitions. The article reviews the application of the Ginzburg-Landau approach to rigorous solutions for issues in the structure of a martensitic nucleus based on the martensitic nucleation theory. The three basic behavior modes of martensitic growth, such as elastic, elastic/plastic, and fully plastic are discussed. The article also reviews the overall kinetics of martensitic transformations.

Sintering provides the interparticle bonding that generates the attractive forces needed to hold together the otherwise loose ceramic powder mass. It also improves hardness, strength, transparency, toughness, electrical conductivity, thermal expansion, magnetic saturation, corrosion resistance, and other properties. This article discusses the fundamentals of sintering and its effects on pore structures and particle density. It addresses some of the more common sintering methods, including solid-state, liquid-phase, and gas pressure sintering, and presents alternative processes such as reaction sintering and self-propagating, high-temperature synthesis. It also describes several pressure densification methods, including hot isostatic pressing, gas pressure sintering, molten particle deposition, and sol-gel processing. The article concludes with a section on grain growth that discusses the underlying mechanisms and kinetics and the relationship between grain growth and densification.