Morphological Stability of Moving Interfaces

As a first approximation, it is assumed that the radial flux entering the edge is constant over the cylindrical interface. The Stefan condition, integrated over the interface, is then 

Integration then produces the linear growth expression 

An expression of the same linear form will be obtained for the growth of a needle if the tip is modeled as a hemisphere. Further results bearing on the diffusion- or interface-limited growth (and shrinkage) of particles have been reviewed by Sutton and Balluffi [6]. 

In the moving-boundary problems treated above, it was assumed that the interface retained its basic initial shape as it moved. It is important to realize that such problems are a subset of a much wider class of problems known as free-boundary problems, in which the boundary is allowed to change its shape as a function of time [2]. A mathematically correct solution for the motion of a boundary of a fixed ideal shape is no guarantee that it is physically realistic. 

1 Stability of Liquid/Solid Interface during Solidification of a Unary System 

---

Let us finally comment on the morphological stability of the boundaries during metal oxidation (A + -02 = AO) or compound formation (A+B = AB) as discussed in the previous chapters. Here it is characteristic that the reaction product separates the reactants. 1 vo interfaces are formed and move. The reaction resistance increases with increasing product layer thickness (reaction rate 1/A J). The boundaries of these reaction products are inherently stable since the reactive flux and the boundary velocity point in the same direction. The flux which causes the boundary motion pushes the boundary (see case c) in Fig. 11-5). If instabilities are occasionally found, they are not primarily related to diffusional transport. The very fact that the rate of the diffusion controlled reaction is inversely proportional to the product layer thickness immediately stabilizes the moving planar interface in a one-... 

Another solid state reaction problem to be mentioned here is the stability of boundaries and boundary conditions. Except for the case of homogeneous reactions in infinite systems, the course of a reaction will also be determined by the state of the boundaries (surfaces, solid-solid interfaces, and other phase boundaries). In reacting systems, these boundaries are normally moving in space and their geometrical form is often morphologically unstable. This instability (which determines the boundary conditions of the kinetic differential equations) adds appreciably to the complexity of many solid state processes and will be discussed later in a chapter of its own. 

Normally, it is not possible to obtain analytical solutions for this transport problem and so we cannot a priori calculate the reaction path. Kirkaldy [J. S. Kirkaldy, D. J. Young (1985)] did pioneering work on metal systems, based on investigations by C. Wagner and the later work of Mullins and Sekerka. They used the diffusion path concept to formulate a number of stability rules. These rules can explain the facts and are predictive within certain limits if applied properly. One of Kirkaldy s results is this. The moving interface in a ternary system is morphologically stable if... 

---