Abstract
Most ceramics are multicomponent materials and the most stable phase at any temperature will be the one with the lowest free energy, G. One use of phase diagrams is to represent the phase or phases we might expect to be present as a function of temperature. There are a large number of books just concerned with this one topic. Much work was carried out in the 1950s and 1960s, but many systems have remained almost completely unexplored and it is not a well-funded area in the United States now. The lack of effort is in spite of the demonstration that new complex ceramics, such as the high-temperature superconductors YBCO and BiSCCO and the magnetic manganates, possess extraordinary, and potentially very useful, properties.
Much of the classical work on phase equilibria has actually been concerned with processing metals. Thus the Fe-O phase diagram is perhaps the most thoroughly characterized because of its importance to the iron and steel industry.
A word to keep in mind throughout our discussion is equilibrium: we are talking about equilibrium phase diagrams. Often we use a phase diagram as a guide to processing. If the process is in progress then it is not in equilibrium. And, by definition, a chemical reaction is not an equilibrium process. If a reaction is exothermic then a rise in temperature favors the reactants. Although most of the phase diagrams we use in ceramics are for a pressure of 1 atmosphere, in one-component systems such as carbon, pressure is a very important variable. It tells us what pressure we need for direct synthesis of diamond. In metal-oxygen diagrams the partial pressure of oxygen determines what is the stable form of the oxide.
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General References
Bergeron, C.G. and Risbud, S.H. (1984) Introduction to Phase Equilibria in Ceramics, The American Ceramic Society, Westerville, OH. This should be available in every ceramics laboratory.
DeHoff, R.T. (2006) Thermodynamics in Materials Science, 2nd edition, CRC, Boca Raton, FL.
Gaskell, D.R. (2003) Introduction to the Thermodynamics of Materials, 4th edition, Taylor & Francis, New York.
Hummel F.A. (1984) Phase Equilibria in Ceramic Systems, Marcel Dekker, New York.
McHale, A.E. (1998) Phase Diagrams and Ceramic Processes, Chapman & Hall, New York.
Muan, A. and Osborn, E.F. (1965) Phase Equilibria among Oxides in Steelmaking, Addison-Wesley Publishing. Co., Reading, MA. Reference for experimental determination of phase diagrams in ceramics. Inspirational with very helpful commentary; a “must see” text.
Phase Diagrams for Ceramists, Vols. I–VIII, The American Ceramic Society, Columbus, OH: I (1964) edited by E.M. Levin, C.R. Robbins, and H.F. McMurdie II (1969) edited by E.M. Levin, C.R. Robbins, and H.F. McMurdie III (1973) edited by E.M. Levin and H.F. McMurdie IV (1981) edited by R.S. Roth, T. Negas, and L.P. Cook V (1983) edited by R.S. Roth, T. Negas, and L.P. Cook VI (1987) edited by R.S. Roth, J.R. Dennis, and H.F. McMurdie Volumes I–VI include mostly oxide and metal + oxide systems. VII (1989) edited by L.P. Cook and H.F. McMurdie (halide systems, many calculated diagrams with methods discussed) VIII (1990) edited by B.O. Mysen (geological, high pressure, and hydrothermal systems)
Under a new series title, but continuous numbering, Phase Equilibria Diagrams, Vols. IX–XII: IX (1992) “Semiconductors and Chalcogenides,” edited by G.B. Stringfellow X (1994) “Borides, Carbides, and Nitrides,” edited by A.E. McHale XI (1995) “Oxides,” edited by R.S. Roth XII (1996) “Oxides,” edited by A.E. McHale and R.S. Roth
Also a part of this series are Phase Equilibrium Diagrams, Annuals’ 91,’ 92, and’ 93, edited by A.E. McHale (these annuals contain a number of complex oxide systems), and Phase Diagrams for High Tc Superconductors, edited by J.D. Whitler and R.S. Roth (1991).
Ragone, D.V. (1995) Thermodynamics of Materials, Volume I, Wiley, New York.
Swalin, R.A. (1972) Thermodynamics of Solids, 2nd edition, Wiley, New York.
Specific References
CALPHAD [computer file], Elsevier, New York. Available in many university libraries on line.
Ellingham, H.J.T. (1944) “Reducibility of oxides and sulfides in metallurgical processes,” J. Soc. Chem. Ind. (London) 63, 125.
Hazen, R.M. (1999) The Diamond Makers, Cambridge University Press, Cambridge. Attaining the high pressures.
Richardson, F.D. and Jeffes, J.H.E. (1948) “The thermodynamics of substances of interest in iron and steel making from 0°C to 2400°C,” J. Iron Steel Inst. (London) 160, 261.
Saunders, N. and Miodownik, A.P. (1988) CALPHAD (Calculation of Phase Diagrams): A Comprehensive Guide, Pergamon, Oxford.
Torres, F.C. and Alarcón, J. (2004) “Mechanism of crystallization of pyroxene-based glass-ceramic glazes,” J. Non-Cryst. Sol. 347, 45.
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(2007). Equilibrium Phase Diagrams. In: Ceramic Materials. Springer, New York, NY. https://doi.org/10.1007/978-0-387-46271-4_8
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