The effective heat of formation (pH') concept allows heats of formation to be calculated as a function of concentration. In this work the effective heat of formation rule is used to predict first phase formation in metal-aluminum thin-film systems and to predict subsequent phase sequence for thin metal films on thick aluminum or thin aluminum on thick metal substrates. The effective concentration at the growth interface is taken to be that of the lowest temperature eutectic (liquidus) for the binary system. Although the effective heat of formation rule may predict that formation of a certain phase would lead to the largest free energy change, this phase does not necessarily form at the moving reaction interface if it has difficulty to nucleate. By excluding phases with a large number of atoms per unit cell and which thus have difficulty to nucleate, the effective heat of formation rule successfully predicts first phase aluminide formation for all 15 metal-aluminum binary systems for which experimental data could be found. It is also shown how the effective heat of formation rule can be used to predict formation and decomposition of aluminide phases in contact with each other or in contact with their component metals.
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