The phase diagrams of ternary systems involving two metal components and one oxidant are considered first, the limitations to their use is discussed in relation to the high temperature oxidation of binary alloys. Kinetic diagrams, which are useful to predict the conditions for the stability of the two mutually insoluble oxides as the external scale, are then calculated on the basis of thermodynamic and kinetic data concerning both the alloys and the oxides, assuming the validity of the parabolic rate law. A combination of the two types of diagrams provides a more detail information about the oxidation behavior of binary alloys. The calculation of the diffusion paths, which relate the oxidant pressure to the composition of the system in terms of the alloy components both in the alloy and in the scale during an initial stage of the reaction in the presence of the parabolic rate law, is finally developed.
The oxidation of two two-phase ternary Fe-Cu-Al alloys containing about 5% Al(mole fraction), one Fe-rich and one Cu-rich, were studied at 700℃in 1×105 Pa pure oxygen. The Fe-rich alloy (Fe-15Cu-5Al) shows two quasi-parabolic stages, with a large increase of the parabolic rate constant after about 4 h. The presence of 5% Al does not change greatly the oxidation rate of Fe-15Cu-5Al with respect to a binary Fe-Cu alloy of similar composition, which was quite different from the situation of the same alloys oxidized at 800℃. Oxidation of Fe-15Cu-5Al at 700℃produced an outer layer of iron oxides and an inner layer containing a mixture of copper metal, iron and aluminium oxide. On the contrary, the Cu-rich Fe-85Cu-5Al alloy presents a rather irregular kinetic behavior, with formation of an inner continuous alumina thin layer and a rather irregular outer layer. The outer layer with a rather irregular thickness was mainly composed of a matrix of copper oxides plus some aluminium and iron oxides presenting in the deep part of the layer at certain locations. As a result of the formation of a protective alumina layer, the presence of 5% Al greatly reduced the oxidation rate of Fe-85Cu-5Al with respect to a binary Fe-Cu alloy of similar composition, which was also quite different from the situation of the same alloys oxidized at 800℃. Moreover, the oxidation rate at 700℃of the Fe-85Cu-5Al alloy was much lower than that of Fe-15Cu-5Al alloy due to the same reason..
