Point defects elements

Since irregular structure elements (point defects) such as interstitial atoms (ions) or vacancies must exist in a crystal lattice in order to allow the regular structure elements to move, two sorts of activation energies have to be supplied from a heat reservoir for transport and reaction. First, the energy to break bonds in the crystal... 

Chemical solid state processes are dependent upon the mobility of the individual atomic structure elements. In a solid which is in thermal equilibrium, this mobility is normally attained by the exchange of atoms (ions) with vacant lattice sites (i.e., vacancies). Vacancies are point defects which exist in well defined concentrations in thermal equilibrium, as do other kinds of point defects such as interstitial atoms. We refer to them as irregular structure elements. Kinetic parameters such as rate constants and transport coefficients are thus directly related to the number and kind of irregular structure elements (point defects) or, in more general terms, to atomic disorder. A quantitative kinetic theory therefore requires a quantitative understanding of the behavior of point defects as a function of the (local) thermodynamic parameters of the system (such as T, P, and composition, i.e., the fraction of chemical components). This understanding is provided by statistical thermodynamics and has been cast in a useful form for application to solid state chemical kinetics as the so-called point defect thermodynamics. 

It will be shown that a more elegant and more easily applicable solution of the problem is given by choosing another reference system. Both the dilute alloy and the unperturbed host can be described with respect to a common reference system, which consists of the unperturbed part of the alloy system and for obvious reasons is called void system. This void system allows for a single-site evaluation of the matrix element describing the wind force in electromigration and the t-matrix element required for the calculation of the residual resistivity due to a saddle-point defect. 

Now, suppose that we have a solid solution of two (2) elemental solids. Would the point defects be the same, or not An easy way to visualize such point defects is shown in the following diagram, given as 3.1.3. on the next page. It is well to note here that homogeneous lattices usually involve metals or solid solutions of metals (alloys) in contrast to heterogeneous lattices which involve compounds such as ZnS. 

Figure 1.2 Point defects in a pure monatomic crystal of an element M, a vacancy, VM, and a self-interstitial, Mj.

Compounds are made up of atoms of more than one chemical element. The point defects that can occur in pure compounds parallel those that occur in monatomic materials, but there is an added complication in this case concerning the composition of the material. In this chapter discussion is confined to the situation in which the composition of the crystal is (virtually) fixed. Such solids are called stoichiometric compounds. (The situations that arise when the composition is allowed to vary are considered in Chapter 4 and throughout much of the rest of this book. This latter type of solid is called a nonstoichiometric compound.) The composition problem can be illustrated with respect to a simple compound such as sodium chloride. 

The notion of point defects in an otherwise perfect crystal dates from the classical papers by Frenkel88 and by Schottky and Wagner.75 86 The perfect lattice is thermodynamically unstable with respect to a lattice in which a certain number of atoms are removed from normal lattice sites to the surface (vacancy disorder) or in which a certain number of atoms are transferred from the surface to interstitial positions inside the crystal (interstitial disorder). These forms of disorder can occur in many elemental solids and compounds. The formation of equal numbers of vacant lattice sites in both M and X sublattices of a compound M0Xft is called Schottky disorder. In compounds in which M and X occupy different sublattices in the perfect crystal there is also the possibility of antistructure disorder in which small numbers of M and X atoms are interchanged. These three sorts of disorder can be combined to give three hybrid types of disorder in crystalline compounds. The most important of these is Frenkel disorder, in which equal numbers of vacancies and interstitials of the same kind of atom are formed in a compound. The possibility of Schottky-antistructure disorder (in which a vacancy is formed by... 

The second type of impurity, substitution of a lattice atom with an impurity atom, allows us to enter the world of alloys and intermetallics. Let us diverge slightly for a moment to discuss how control of substitutional impurities can lead to some useful materials, and then we will conclude our description of point defects. An alloy, by definition, is a metallic solid or liquid formed from an intimate combination of two or more elements. By intimate combination, we mean either a liquid or solid solution. In the instance where the solid is crystalline, some of the impurity atoms, usually defined as the minority constituent, occupy sites in the lattice that would normally be occupied by the majority constituent. Alloys need not be crystalline, however. If a liquid alloy is quenched rapidly enough, an amorphous metal can result. The solid material is still an alloy, since the elements are in intimate combination, but there is no crystalline order and hence no substitutional impurities. To aid in our description of substitutional impurities, we will limit the current description to crystalline alloys, but keep in mind that amorphous alloys exist as well. 

As mentioned above, the non-stoichiometric compounds originate from the existence of point defects in crystals. Let us consider a crystal consisting of mono-atoms. In ideal crystals of elements, atoms occupy the lattice points regularly. In real crystals, on the other hand, various kinds of point defects can exist in thermodynamic equilibrium. First, we shall consider vacancies , which are empty regular lattice points. Consider a crystal composed of one element which has N atoms sited on regular lattice points and vacancies,... 

From consideration of the point defects of elements mentioned in Section 1.3.1, the nature of the point defects of compounds MX, where M is metal and X is O, S, N, H (volatile elements) etc., can be easily understood. Possible point defects of the compounds MX are as follows ... 

The number of interstitial atoms Np in the Frenkel type and the number of vacancies TYj in the Schottky type at thermal equilibrium can be obtained, following a similar calculation to that for the concentration of point defects of elements mentioned in Section 1.3.1, as... 

In retrospect, one can understand why solid state chemists, who were familiar with crystallographic concepts, found it so difficult to imagine and visualize the mobility of the atomic structure elements of a crystal. Indeed, there is no mobility of these particles in a perfect crystal, just as there is no mobility of an individual car on a densely packed parking lot. It was only after the emergence of the concept of disorder and point defects in crystals at the turn of this century, and later in the twenties and thirties when the thermodynamics of defects was understood, that the idea... 

The resulting equilibrium concentrations of these point defects (vacancies and interstitials) are the consequence of a compromise between the ordering interaction energy and the entropy contribution of disorder (point defects, in this case). To be sure, the importance of Frenkel s basic work for the further development of solid state kinetics can hardly be overstated. From here on one knew that, in a crystal, the concentration of irregular structure elements (in thermal equilibrium) is a function of state. Therefore the conductivity of an ionic crystal, for example, which is caused by mobile, point defects, is a well defined physical property. However, contributions to the conductivity due to dislocations, grain boundaries, and other non-equilibrium defects can sometimes be quite significant. 

In 1937, dost presented in his book on diffusion and chemical reactions in solids [W. lost (1937)] the first overview and quantitative discussion of solid state reaction kinetics based on the Frenkel-Wagner-Sehottky point defect thermodynamics and linear transport theory. Although metallic systems were included in the discussion, the main body of this monograph was concerned with ionic crystals. There was good reason for this preferential elaboration on kinetic concepts with ionic crystals. Firstly, one can exert, forces on the structure elements of ionic crystals by the application of an electrical field. Secondly, a current of 1 mA over a duration of 1 s (= 1 mC, easy to measure, at that time) corresponds to only 1(K8 moles of transported matter in the form of ions. Seen in retrospect, it is amazing how fast the understanding of diffusion and of chemical reactions in the solid state took place after the fundamental and appropriate concepts were established at about 1930, especially in metallurgy, ceramics, and related areas. 

We have discussed point defects in elements (A) and in nearly stoichiometric compounds having narrow ranges of homogeneity. Let us extend this discussion to the point defect thermodynamics of alloys and nonmetallic solid solutions. This topic is of particular interest in view of the kinetics of transport processes in those solid solutions which predominate in metallurgy and ceramics. Diffusion processes are governed by the concentrations and mobilities of point defects and, although in inhomogeneous crystals the components may not be in equilibrium, point defects are normally very close to local equilibrium. 

AX at the AY/AX boundary. The main feature of this interface reaction (i.e., the transport of building elements across b) is the injection of mobile point defects into available vacant sites and the subsequent local relaxation towards equilibrium distributions. According to Figure 10-9 b, two different modes of cation injection can take place in the relaxation zone R. 1) Cations are injected into the sublattice of predominant ionic transference in AX by the applied field. In this case, no further defect reaction is necessary for the continuation of cation transport. 2) Cations are injected into the wrong sublattice which does not contribute noticeably to the cation transport in AX. Defect reactions (relaxation) will occur subsequently to ensure continuous charge transport. This is the situation depicted in Figure 10-9b, and, in view of its model character, we briefly outline the transport formalism. 

AC/ is known as the overpotential in the electrode kinetics of electrochemistry. Let us summarize the essence of this modeling. If we know the applied driving forces, the mobilities of the SE s in the various sublattices, and the defect relaxation times, we can derive the fluxes of the building elements across the interfaces. We see that the interface resistivity Rb - AC//(F-y0) stems, in essence, from the relaxation processes of the SE s (point defects). Rb depends on the relaxation time rR of the (chemical) processes that occur when building elements are driven across the boundary. In accordance with Eqn. (10.33), the flux j0 can be understood as the integral of the relaxation (recombination, production) rate /)(/)), taken over the width fR. 

The influence of plastic deformation on the reaction kinetics is twofold. 1) Plastic deformation occurs mainly through the formation and motion of dislocations. Since dislocations provide one dimensional paths (pipes) of enhanced mobility, they may alter the transport coefficients of the structure elements, with respect to both magnitude and direction. 2) They may thereby decisively affect the nucleation rate of supersaturated components and thus determine the sites of precipitation. However, there is a further influence which plastic deformations have on the kinetics of reactions. If moving dislocations intersect each other, they release point defects into the bulk crystal. The resulting increase in point defect concentration changes the atomic mobility of the components. Let us remember that supersaturated point defects may be annihilated by the climb of edge dislocations (see Section 3.4). By and large, one expects that plasticity will noticeably affect the reactivity of solids. 

---