Solid state intermetallic structures

Metallurgists originally, and now materials scientists (as well as solid-state chemists) have used erystallographic methods, certainly, for the determination of the structures of intermetallic compounds, but also for such subsidiary parepistemes as the study of the orientation relationships involved in phase transformations, and the study of preferred orientations, alias texture (statistically preferential alignment of the crystal axes of the individual grains in a polycrystalline assembly) however, those who pursue such concerns are not members of the aristocracy The study of texture both by X-ray diffraction and by computer simulation has become a huge sub-subsidiary field, very recently marked by the publication of a major book (Kocks el al. 1998). 

Bis[2-(diphenylphosphino)phenyl]phenylphosphine (TP) is a very inflexible ligand with a rigid backbone and gives the trinuclear complex [Au3Cl3(TP)] (452), that has a compact unsymmetrical structure in the solid state which is retained in solution owing to the fixation of the gold atoms through intermetallic contacts.2651... 

Vaughey J. T., O Hara J., Thackeray M. M., Intermetallic insertion electrodes with a zinc blende-type structure for Li Batteries A study of LixInSb (0 <= x <= 3), Electrochem. and Solid State Lett., (2000) 3 (1), 13-16. 

Another characteristic point is the special attention that in intermetallic science, as in several fields of chemistry, needs to be dedicated to the structural aspects and to the description of the phases. The structure of intermetallic alloys in their different states, liquid, amorphous (glassy), quasi-crystalline and fully, three-dimensionally (3D) periodic crystalline are closely related to the different properties shown by these substances. Two chapters are therefore dedicated to selected aspects of intermetallic structural chemistry. Particular attention is dedicated to the solid state, in which a very large variety of properties and structures can be found. Solid intermetallic phases, generally non-molecular by nature, are characterized by their 3D crystal (or quasicrystal) structure. A great many crystal structures (often complex or very complex) have been elucidated, and intermetallic crystallochemistry is a fundamental topic of reference. A great number of papers have been published containing results obtained by powder and single crystal X-ray diffractometry and by neutron and electron diffraction methods. A characteristic nomenclature and several symbols and representations have been developed for the description, classification and identification of these phases. 

The situation in the solid state is generally more complex. Several examples of binary systems were seen in which, in the solid state, a number of phases (intermediate and terminal) are formed. See for instance Figs 2.18-2.21. Both stoichiometric phases (compounds) and variable composition phases (solid solutions) may be considered and, as for their structures, both fully ordered or more or less completely disordered phases. This variety of types is characteristic for the solid alloys. After a few comments on liquid alloys, particular attention will therefore be dedicated in the following paragraphs to the description and classification of solid intermetallic phases. 

In the previous chapter we looked at some questions concerning solid intermetallic phases both terminal (that is solubility fields which include one of the components) and intermediate. Particularly we have seen, in several alloy systems, the formation in the solid state of intermetallic compounds or, more generally, intermetallic phases. A few general and introductory remarks about these phases have been presented by means of Figs. 2.2-2.4, in which structural schemes of ordered and disordered phases have been suggested. On the other hand we have seen that in binary (and multi-component) metal systems, several crystalline phases (terminal and intermediate, stable and also metastable) may occur. 

As a starting point in the description of the solid intermetallic phases it is useful to recall that their identification and classification requires information about their chemical composition and structure. To be consistent with other fields of descriptive chemistry, this information should be included in specific chemical and structural formulae built up according to well-defined rules. This task, however, in the specific domain of the intermetallic phases, or more generally in the area of solid-state chemistry, is much more complicated than for other chemical compounds. This complexity is related both to the chemical characteristics (formation of variable composition phases) and to the structural properties, since the intermetallic compounds are generally non-molecular in nature, while the conventional chemical symbolism has been mainly developed for the representation of molecular units. As a consequence there is no complete, or generally accepted, method of representing the formulae of intermetallic compounds. 

An ordered distribution of spheres of different sizes always allows a better filling of space the atoms are closer together, and the attractive bonding forces become more effective. As for the structures of other types of compound, we observe the validity of the principle of the most efficient filling of space. A definite order of atoms requires a definite chemical composition. Therefore, metal atoms having different radii preferentially will combine in the solid state with a definite stoichiometric ratio they will form an intermetallic compound. 

Another interesting feature of the dinuclear iridium complex [IrCl(PF3)2]2 is its very dark color and metallic luster in the solid state, indicative of intermetallic bonding. A recent single-crystal structure determination (149) reveals that the structure consists of infinite zigzag chains of iridium atoms with short inter- and intramolecular Ir Ir contacts (see Figs. 15 and 16). 

Fransson, L.M.L., Vaughey, J.T., Edstrom, K., and Thackeray, M.M., Structural transformations in intermetallic electrodes for lithium batteries an in situ x-ray diffraction study of lithiated MnSb and Mn2Sb, J. Electrochem. Soc., 150, A86, 2003. Yang, J., Wachtler, M., Winters, M., and Besenhard, J.O., Sub-microcrystalline Sn and Sn-SnSb powders as lithium storage materials for lithium-ion batteries, Electrochem. Solid State Lett., 2, 161, 1999. 

Alloy systems have been known to man since the Bronze Age. It is, however, only in recent times that they have been the subject of systematic studies, and in these studies no tool has proved more powerful than the technique of crystal structure analysis. Indeed, the extension of our knowledge and understanding of the properties of intermetallic systems to which it has given rise is one of the greatest achievements of crystal chemistry. Prior to the application of X-ray methods, the investigation of the properties of alloy systems was confined principally to observations of their behaviour in the liquid state, and the behaviour of the metal as a solid could be determined only by inference from these observations. Transitions in the solid state and the effect of mechanical or heat treatment could not, of course, be observed in this way, and for information on these properties the microscope and other purely physical methods had to be invoked. Even so, these methods were all more or less indirect, and it is only since the application of X-ray analysis that it has been possible to investigate directly in the solid state, under the precise conditions which are of technical interest and without damage to the specimen, the exact positions of all the atoms in the structure, and so to refer to their ultimate cause the physical and chemical properties of the alloy. 

---