Part IX - Surface Self-Diffusion of Gold(l): Analysis of the Scratch-Flattening Process

The formal descnption of the decay of an isolated scratch can be written in terms of an appropriate Fourier integral. With the application of certain approximations, this description leads to the second-moment analysis developed by King and Mullins. It is shown that the second-moment analysis does not adequately describe the behavior of a decaying, isolated scratch, and that it is difficult to obtain internally consistent values of the surface self-diffusion coefficient, D,,from this analysis. This inconsistency arises from contributions of higher-order moments to the decay process. Two new analytical methods, based on the Fourier integval representation of a scratch profile, have been developed for determining values of D, from the decay kinetics of isolated scratches. In the profile-matching method, a given initial profile is resolved into its Fourier components, the components are allowed to decay exponentially over an annealing time interval, At, and finally they are synthesized to form a decayed profile. The predicted profile is adjusted to fit the experimental profile by varying only the parameter, D,At; the contribution from volume diffusion is directly taken into account and the integrals involved in the Fourier analysis are evaluated by numerical integration on an electronic computer. In the kinetic method, the widths, W, of a series of predicted profiles are determined for various volume-diffusion contributions, and the results are plotted in the form W vs DSAt. For a fixed ratio of surface to volume diffusivities, R, these plots are linear; the slope of the lines increases as R decreases. A simi-lar analysis can be performed on the depths of the predicted profiles. In this case, plots of (l/df3 vs D,At are found to be nonlinear. The proper value of Ds is found by superimposing the data for the experimental widths and depths on Plots of this kind and adjusting Ds until a fit is obtained with the line having the appropriate value oj R. An analysis of the slopes of these plots for R —= (surface diffusion only) reveals that they do not give the correct value, 2276, for width tf second-moment standard profile. This finding allows one to modify the second-moment analysis in such a way as to obtain internally consistent values of Ds. ThERE are several processes, involving a flow of matter along a surface, due to gradients in curvature of the surface, that may be used to determine the surface self-diffusion coefficient, Ds. These processes are commonly known as 1) thermal grooving, 2) single and 3) multiple scratch decay, 4) blunting of field-emitter tips, and 5) sintering. In this series of papers, the first three of these processes are examined in detail in an attempt to subject the phenomenological theories governing these processes to a critical test and, furthermore, to make a critical comparison of the values of D, obtained from these techniques. Although the thermal grooving technique has been established'' as a reliable method for determining D, , this has not been the case for the process of scratch flattening. Mullins and coworkers374 have proposed phenomenological laws governing the growth of the width and the decay of the amplitude of an isolated scratch, but only in one study5 has the width-growth law been supported by experimental evidence. In paper I of this series detailed experimental evidence is presented that points up the deficiencies of the second-moment analysis; the origins of these deficiencies are also discussed. Following this development, some new analytical procedures, based on representing the scratch profile by Fourier integrals, are presented as a means of obtaining reliable values of D, from the kinetics of the scratch-flattening process. Further applications of the Fourier integral approach are reported in papers 11' and 111,~ where the method has been useful in interpreting the anisotropy of flattening rates of isolated scratches (paper 11) and in describing the multiple scratch decay process (paper 111). THEORY OF SCRATCH DECAY Following ~ullins" approach we consider an arbitrarily shaped scratch profile, Fig. 6, at some time, t. The profile is designated by a function z(x,t) which can be expressed in terms of a Fourier integral as follows: