Defect Structure of Oxides When a metal is exposed to an oxidizing environment, an initial thin film of oxide is formed first, which covers the whole surface. As the oxide layer grows further, either the metal ions from the substrate or oxygen ions from the atmosphere must pass through the initial thin film, Transport of the ions through the oxide film usually occurs via solid state diffusion, which in turn depends upon the imperfections in the solid or its defect structure. Knowledge of the defect structure is, therefore, important to understand the growth of the oxide scales. Although both these topics are inter-related, defect structure of the solids is discussed first in this chapter, followed by the diffusion in solids, in the subsequent chapter. PERFECT CRYSTAL A perfect crystalline solid is one in which all the lattice positions are occupied by the respective atoms, cations or anions, In principle, perfect solids exist only at the absolute zero temperature, It is now well established that most solids at a temperature above absolute zero have some kinds of defects. When the crystal lattice of a solid has cither missing atoms or atoms which are displaced from their lattice positions, the solid is called an imperfect solid Point Defects and the most prominent point defects in an oxide are: ich defects are called Vacancies: formed as a result of a missing metal ion or oxygen anion from the lattice; Interstitials: formed as a result of the displacement of oxygen or metal ions from their lattice positions; Impurities: formed as a result of cations substituted by foreign cations. In addition, there are electronic defects, quasi free electrons and electron holes, to compensate the charge balance due to formation of point defects ‘There are other types of imperfections also, such as line defects and surface defects, which will not be considered here, This chapter will deal only with point defeets. Notation of Point Defects The very first thing to learn about the defect structure is to know how to describe a defect Many systems have been used to describe the defects. But the most accepted system today is that given by Kroeger and Vink. In this system, which is now accepted by the International Union of Pure and Applied Chemistry (IUPAC), the type of defect and its position in thelattice are described by a symbol followed by a subscript. For an oxide, the various defects are written as: V,, — oxygen vacancy Vm — metal vacancy 0; — oaygen interstitial ‘M, — metal interstitial In principle, all types of defects are possible in a solid, However, the free energy of the formation of different types of defects has widely different values, and correspondingly one type of defect structure commonly predominates in a particular solid, The relative concentration of different types of defects is a function of temperature and other variables which influence the state and composition of the solid. Point defects may be neutral or charged. The charge of a defeet is always indicated as the effective charge, i.e. the charge expressed with reference to the charge normally present in the same position in the host lattice. In the Kroeger Vink notation, the effective charge indicated by a superscript; a dot(.) for each unit of positive charge, a prime (’) for each unit of negative charge and across (x) for a neutral defect (effective charge of zero). For example: OG — represents an oxygen atom on its normal lattice position; 05 — represents an oxygen vacancy with an effective charge of +2; represents a metal vacancy with an effective charge of -1; represents an interstitial oxygen ion; represents an interstitial metal ion with valance +2 tion of valance +2 on M** site, Oj, — represents a foreign c: An electron in the lattice is represented by & [M'] and electron hole as [My] Concentration of defects are written in square brackets e.g. [V;'] indicates the concentration of doubly charged oxygen vacancies, In the case of electrons and holes, the concentrations are written as n and p instead of é or h respectively. Figure 2.1 illustrates the two most common defects, found in solids: the Frenkel defect, acation vacancy, and an interstitial and Schottky defect, a pair of cation and anion vacancy. In addition to Schottky and Frenkel disorders, other possible defects ean beA pair of interstitial atoms, Ort My Displaced atoms Om + My Vacancy and misplaced atoms Vg +My Interstitial and misplaced atoms My" + Ow However, these defects are found to be of little importance in comparison to the most common Schottky and Frenkel disorders. For a long time, it was believed that inorganic compounds had a definite composition, 26 Introduction to High Temperature Oxidation and Corrosion Fig. 2.1 (a) Frenkel defect and (b) Sehottky defect. determined by the valance of atoms as per Dalton’s law and that the atoms were arranged in an ideal and completely ordered structure, with all lattice sites occupied. In the early 1900°s, however, it was recognised that many inorganic compounds, in fact had a variable composition and today it is well established that an exact stoichiometric composition exists only at a definite partial pressure of the components ata given temperature. Deviation from stoichiometric composition icaled onset This is especially important for those oxides where cations exist in several valance states. Some of the examples are the oxides of transition metals, FeO, MnO, NiO and CoO, rare earth oxides CeO, ete. and actinide oxides, UO, Pu, ete. In nonstoichiometric oxides, defects are often confined either to the oxygen or metal lattice. They can therefore be classified as those containing predominantly oxygen defects or those having cation defects.Oxides with Anion Defects ‘These may have either an excess of oxygen or adeticit in oxygen, Oxides with excess oxygen may be written as MO,,, where x is a small fraction of a. Excess oxygen is located at an wrstitial position of the oxide lattice, UO>,, is an example of an oxide with anion defects where excess oxygen is found on the interstitial position. Oxygen deficient oxides are represented by a general formula MO, ,. where y is a small fraction of a. In such oxides, point defects are oxygen vacancies e.g. Nb3Os and Ta,Os, Oxides with Cation Defects Oxides with cation defects may have either an excess or deficit in metal, relative to the stoichiometric composition. Oxides, with excess metal, can be represented by Mj..,0, where Mla small fraction of. The excoss metal occupies an infexstitil position, eg. ZnO, Metal deficit oxides; which may be written as M,,..0, where'm la small fraction of b, have metal vacancies, Examples of such oxides are, FeO, NiO, CoO ete. ‘There are several examples, where disorder in the oxide is on both anion and cation lattice sites. TiO and NbO are examples of such oxides. In TiO, one of every seven of both cation and anion lattices is vacant, while for NbO, 25% of both the cation and anion sites are vacant Certain oxides, such as MgO and AI,O, have very little deviation from stoichiometry. Such oxides are called near stoichiometric oxides, and they are characterized by their high density in comparison to the metal, and have in general close packed structures. FORMATION OF DEFECTS In contrast to the Schottky and Frenkel disorder, most defects in the nonstoichiometric oxides are formed by reaction with the atmosphere. The type of oxides that are usually formed i a given oxide depend on the possible valence state of the cations. If these are easily reduced to a lower state, then oxygen vacancies will generally be formed, for example in the case of CeO>, If on the other hand, the cation can be oxidised to a higher valence state, as in FeO, then metal vacancies will be the dominant type of defects. Let us now consider some examples of defect formation in different types of oxides. However prior to doing so, it is important to learn the rules for w before learning how they are formed. Ther writing a defect reaction, These are: ‘ing defect reaction, are three rules which must be followed, while