1 Thermodynamics and Phase Dingrams of Materials rR aa Teng, ee Poni, ia yee un Ain Ce in tin Se tye ara ‘ene {S12 Topo Boar Pe lage nnnpation Terma He ia a ‘Ragman Repenson Eco ope ‘tat cate Ps ns StSitean stag etme Sota | ‘ati ig pain hey Cn i ‘epi erry hr Seon Sse eee fee ge gueeuuess nantees gases 1s of Syms dress Secale ‘eal a Soe on Soon =1.1 Introduction ‘An understanding of thermodynamics and phase diagrams is fundamental and essential to the study of materials science. ‘A knowledge of the equilibrium state un- der a given sct of conditions is the starting point in the description of any phenome- non oF process. ‘The theme of this chapter is the relation- ship between phase diagrams and thermo- dynamics. A phase diagram is a graphical representation of the values of thermody- namic variables when equilibrium is estab- lished among the phases of a system. Mate- rials scientists are accustomed to think of phase diagrams as plots of temperature versus composition. However, many other variables such as total pressure and partial pressures may be plotted on phase dia- grams. In Sec. 1.3, for example, predomi- nance diagrams will be discussed, and in Sec. 1.7 chemical potential-composition phase diagrams will be presented. General rules for classifying phase diagrams are given in Sec. 1.10. In recent years, a quantitative coupling of thermodynamics and phase diagrams hhas become possible. With the use of com- puters, simultaneous optimizations of ther- modynamic and phase equilibrium data can be applied to the critical evaluation of binary and ternary systems as shown in See. 1.6. This approach often permits good estimations to be made of the thermody- namic properties and phase diagrams of multicomponent systems as discussed in See. 1.9. These estimations are based upon structural models of solutions. Various models such as the regular solution model, the sublattice model for ionic systems, and models for interstitial solutions, polymeric solutions, solutions of defects, ordered so- lutions, ete: are discussed in Sees, 1.5 and 18, 1.2 Gibbs Energy and Equilibrium 5 ‘The equilibrium diagram is always cal- culated by minimization of the Gibbs energy. General computer programs are available for the minimization of the Gibbs energy in systems of any number of phases, components, and species as outlined in Sec. 4.11. When coupled to extensive databases of the thermodynamic properties of com- pounds and multicomponent solutions, these provide a powerful tool in the study of materials science. LAA Notation Extensive thermodynamic properties are represented by upper case symbols. For example, G= Gibbs energy in J. Molar properties are represented by lower case symbols. For example, g—G/n=molar Gibbs energy in J/mol where m is the total number of moles in the system. 1.2 Gibbs Energy and Equilibrium 1.2.1 Gibbs Energy The Gibbs energy of a system is defined in terms ofits enthalpy, H, entropy S, and temperature, T: G=H-TS a) A system at constant temperature and pressure will approach an equilibrium state which minimizes G. ‘As an example, consider the question whether silica fibers in an aluminum ma- trix at 500°C will react to form mullite, AlgSinO 3 Bsio, + 6at Si+ALSiO13 (1-2) 2 Ifthe reaction proceeds with the formation of dn moles of mullite then, from the stoi- chiometry of the reaction, ds = (9/2)dn, dng, = —6dan, and drigio, = ~13/2dn. Since