Solid intermetallic phases crystal structure

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. 

Notes on the alloy crystal chemistry of the 6th group metals. A selection of the intermetallic phases, and of their structures, formed by Cr, Mo and W is shown in Table 5.35. Attention has been given in this list to the presence of several tetrahedrally close-packed alloys, often corresponding to ranges of solid solutions. 

The circumstances under which intermetallics form were elucidated by the British metallurgist William Hume-Rothery (1899-1968) for compounds between the noble metals and the elements to their right in the periodic table (Hume-Rothery, 1934 Reynolds and Hume-Rothery, 1937). These are now applied to all intermetaUic compounds, in general. The converse to an intermetaUic, a solid solution, is only stable for certain valence-electron count per atom ratios, and with minimal differences in the atomic radii, electronegativities, and crystal structures (bonding preferences) of the pure components. For example, it is a mle-of-thumb that elements with atomic radii differing by more than 15 percent generally have very little solid phase miscibility. 

At present a large variety of solid compounds are called Zintl phases. The name Zintl phase was introduced by Laves According to Laves, Zintl phases are those intermetallic compounds which crystallize in typical non-metal crystal structures. For these compounds one expects an ionic contribution to the chemical bond. This definition has been extended to a large number of solid compounds formed by alkali or alkaline earth metals with metallic or semimetallic elements of the fourth, fifth and partly third group of the Periodic Table for which common structural and bonding properties have been found. The crystal structures and chemical properties of these compounds have been studied extensively . ... 

Both silver and gold form ideal solid solutions with palladium. However, stoichiometric compositions with unique properties, such as in Hunter s preferred membrane composition of PdsAg, [31], might suggest the possibility of intermetallic compounds or ordered structures differing from that of the ideal solutions [35]. Palladium and copper also form ideal solid solutions, but in this system phase diagrams clearly show additional phases with crystal structures differing from the parent fee phase of the solid solutions. 

Landolt-Bornstein, Numerical Data and Functional Relationships in Science and Technology, K.-H. Hellwege (Ed.), Group III. Crystal and Solid State Physics, Vol. 6, Structure Data of Elements and Intermetallic Phases, P. Eckerlin, H. Kandler, and A. Stegher (Eds), Springer, Berlin, 1971. 

Aluminium-Copper. Al-Cu forms a simple eutectic system in the range Irom 0 to 53wt% Cu, as shown in Fig. 3.1-11. The a-Al solid solution and the intermetallic compound AI2Q1 (0 phase) are in equilibrium. At intermediate temperatures, metastable transition phases may form and precipitate from the supersaturated solid solution. These metastable phases may be characterised according to their crystal structure, the nature of the phase boundary they form, and their size ... 

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). 

A variety of defect formation mechanisms (lattice disorder) are known. Classical cases include the - Schottky and -> Frenkel mechanisms. For the Schottky defects, an anion vacancy and a cation vacancy are formed in an ionic crystal due to replacing two atoms at the surface. The Frenkel defect involves one atom displaced from its lattice site into an interstitial position, which is normally empty. The Schottky and Frenkel defects are both stoichiometric, i.e., can be formed without a change in the crystal composition. The structural disorder, characteristic of -> superionics (fast -> ion conductors), relates to crystals where the stoichiometric number of mobile ions is significantly lower than the number of positions available for these ions. Examples of structurally disordered solids are -> f-alumina, -> NASICON, and d-phase of - bismuth oxide. The antistructural disorder, typical for - intermetallic and essentially covalent phases, appears due to mixing of atoms between their regular sites. In many cases important for practice, the defects are formed to compensate charge of dopant ions due to the crystal electroneutrality rule (doping-induced disorder) (see also -> electroneutrality condition). 

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