Binary alloys intermediate phases

Because of the interest in its use in elevated-temperature molten salt electrolyte batteries, one of the first binary alloy systems studied in detail was the lithium-aluminium system. As shown in Fig. 1, the potential-composition behavior shows a long plateau between the lithium-saturated terminal solid solution and the intermediate P phase "LiAl", and a shorter one between the composition limits of the P and y phases, as well as composition-dependent values in the single-phase regions [35], This is as expected for a binary system with complete equilibrium. The potential of the first plateau varies linearly with temperature, as shown in Fig. 2. 

The existence of an approximate relation between the average number of stable intermediate phases in a binary system and the calculated extreme values of the enthalpies of formation was also suggested (see Fig. 2.7). Although the way to predict formation enthalpies of alloys was introduced as an empirical one and several discrepancies may be noticed between calculated and measured values, it is important to observe that the model incorporates basic physics. 

Simple schematic phase diagrams of binary alloy systems are shown in Fig. 2.18 in which the formation of one intermediate solid phase may be noticed. In these... 

Trends in the formation capability of binary compounds. A few general comments about the formation of intermediate phases in binary alloy systems can be made by using maps similar to those previously employed in Fig. 2.8 in order to give a summary of the mutual solubility. 

Figure 2.22. Compound formation capability in binary systems. The different element combinations are mapped on Mendeleev number coordinates and those systems are indicated in which the formation of intermediate phases has been observed (either from the liquid or in the solid state). Blank boxes indicate systems for which no certain data are available. Notice that the compound-forming alloys are crowded in a region corresponding to a large difference in the Mendeleev numbers of the elements involved (for instance, basic metals with semi-metals).

Several phase diagrams of binary alloy systems have been shown (see for instance Fig. 2.18) in which the existence of intermediate phases may be noticed. In these systems we have seen the formation of AmB phases, which generally crystallize with structures other than those of the constituent elements, and which have negligible homogeneity ranges. Thermodynamically, the composition of any such phase is variable. In a number of cases, as those exemplified in Fig. 2.19, the possible variation in composition is very small (invariant composition phases or... 

Table 5.6. A selection of formulae and structure types of intermediate phases in the alkali metal binary alloys (CNE coordination number around the A alkali metal).

Remarks on the crystal chemistry of the alloys of the 3rd group metals. A large number of intermediate phases have been identified in the binary alloys formed by the rare earth metals and actinides with several elements. A short illustrative list is shown in Tables 5.19 and 5.20. Compounds of a few selected rare earth metals and actinides have been considered in order to show some frequent stoichiometries and crystal structure types. The existence of a number of analogies among the different metals considered and the formation of some isostructural series of compounds may be noticed. 

Table 5.19. A selection of intermediate phases in some rare earth binary alloys.

Remarks on the melting point trends in the binary alloys of Be, Mg and of the 12th group metals. The intermetallic reactivity of these metals and the stability of their compounds are also highlighted by the trends of the melting points of their alloys. A selection of these data has been collected in Tables 5.57 and 5.58 where compounds of Be and Mg and of Zn and Hg are listed. For several systems, information only on the existence of intermediate phases with no indication about their melting temperature is reported. 

Owing to their numerous actual and potential applications, several ternary and complex systems of these metals, especially of aluminium, have been investigated a few examples of the systematics of Al-Me-X alloys are presented in 5.18 and in Fig. 5.41. Recent contributions to this subject have been given with the study of the systems R-Al-Cu (Riani et al. 2005, and references there in). These rare earth alloys, characterized by the formation of several intermediate phases, are interesting also as raw materials for the preparation of amorphous alloys. Regularities in the trends of their properties have been underlined. The experimental and calculated data relevant to the binary systems Al-Fe, Al-Ni and Fe-Ni have been examined and discussed in a paper concerning the assessment of the ternary Al-Fe-Ni system (Eleno et al. 2006). 

These problems have of course different weights for the different metals. The high reactivity of the elements on the left-side of the Periodic Table is well-known. On this subject, relevant examples based on rare earth metals and their alloys and compounds are given in a paper by Gschneidner (1993) Metals, alloys and compounds high purities do make a difference The influence of impurity atoms, especially the interstitial elements, on some of the properties of pure rare earth metals and the stabilization of non-equilibrium structures of the metals are there discussed. The effects of impurities on intermetallic and non-metallic R compounds are also considered, including the composition and structure of line compounds, the nominal vs. true composition of a sample and/or of an intermediate phase, the stabilization of non-existent binary phases which correspond to real new ternary phases, etc. A few examples taken from the above-mentioned paper and reported here are especially relevant. They may be useful to highlight typical problems met in preparative intermetallic chemistry. 

Notice that the structures presented in this paragraph are unary structures, that is one species only is present in all its atomic positions. In the prototypes listed (and in the chemically unary isostructural substances) this species is represented by a pure element. In a number of cases, however, more than one atomic species may be equally distributed in the various atomic positions. If each atomic site has the same probability of being occupied in a certain percentage by atoms X and Y and all the sites are compositionally equivalent, the unary prototype is still a valid structural reference. In this case, from a chemical point of view, the structure will correspond to a two-component phase. Notice that there can be many binary (or more complex) solid solution phases having for instance the Cu-type or the W-type structures. Such phases are formed in several metallic alloy systems either as terminal or intermediate phases. 

G.16 W. B. Pearson. A Handbook of Lattice Spacings and Structures of Metals and Alloys (New York Pergamon Press, 1958). A most useful source of information. Gives the crystal structures of intermediate phases, and the variation of lattice parameter with composition in solid solutions, of binary and ternary alloys. Also gives the crystal structures of metal borides, carbides, hydrides, nitrides, and binary oxides. 

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