Anion interstitial creation

Nonequihbrium concentrations of point defects can be introduced by materials processing (e.g. rapid quenching or irradiation treatment), in which case they are classified as extrinsic. Extrinsic defects can also be introduced chemically. Often times, nonstoichiometry results from extrinsic point defects, and its extent may be measmed by the defect concentration. Many transition metal compounds are nonstoichiometric because the transition metal is present in more than one oxidation state. For example, some of the metal ions may be oxidized to a higher valence state. This requires either the introduction of cation vacancies or the creation of anion interstitials in order to maintain charge neutrality. The possibility for mixed-valency is not a prerequisite for nonstoichiometry, however. In the alkah hahdes, extra alkah metal atoms can diffuse into the lattice, giving (5 metal atoms ionize and force an equal number... 

In pure and stoichiometric compounds, intrinsic defects are formed for energetic reasons. Intrinsic ionic conduction, or creation of thermal vacancies by Frenkel, ie, vacancy plus interstitial lattice defects, or by Schottky, cation and anion vacancies, mechanisms can be expressed in terms of an equilibrium constant and, therefore, as a free energy for the formation of defects, If the ion is to jump into a normally occupied lattice site, a term for... 

Figure 4.9 Clusters in the fluorite structure (a, b) transformation of a cube into a square antiprism (c, d) transformation of a cube into a cuboctahedron (e) a single square antiprism formed by tbe creation of < 110> interstitial defects (/) an M6F36 cluster in a fluorite structure matrix. Cations in the plane of tbe section are represented by smaller spheres anions above and below the plane are represented by larger spheres.

TypeC oxides compensate for the lack of metal with interstitial anions. The charge balance is maintained by the creation of two ions for each interstitial anion (c), each of which we can think of as associated with a positive hole. 

The solid M is a binary compound (or more). The reaction of solid-solid interface, always in two steps, creates vacancies of each of the two components and this building unit can either diffuse to the heart or precipitate to create a new solid phase. We will see such an example in Chapter 15 for the creation of oxygen anions in interstitial positions in uranium dioxide dining the reduction of trimanium octoxide. 

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