Varun A. Baheti

Effect of Ni content on the diffusion-controlled growth of the product phases in the Cu(Ni)-Sn system

Abstract A strong influence of Ni content on the diffusion-controlled growth of the (Cu,Ni)3Sn and (Cu,Ni)6Sn5 phases by coupling different Cu(Ni) alloys with Sn in the solid state is reported. The continuous increase in the thickness ratio of (Cu,Ni)6Sn5 to (Cu,Ni)3Sn with the Ni content is explained by combined kinetic and thermodynamic arguments as follows: (i) The integrated interdiffusion coefficient does not change for the (Cu,Ni)3Sn phase up to 2.5 at.% Ni and decreases drastically for 5 at.% Ni. On the other hand, there is a continuous increase in the integrated interdiffusion coefficient for (Cu,Ni)6Sn5 as a function of increasing Ni content. (ii) With the increase in Ni content, driving forces for the diffusion of components increase for both components in both phases but at different rates. However, the magnitude of these changes alone is not large enough to explain the high difference in the observed growth rate of the product phases because of Ni addition. (iv) Kirkendall marker experiments indicate that the Cu6Sn5 phase grows by diffusion of both Cu and Sn in the binary case. However, when Ni is added, the growth is by diffusion of Sn only. (v) Also, the observed grain refinement in the Cu6Sn5 phase with the addition of Ni suggests that the grain boundary diffusion of Sn may have an important role in the observed changes in the growth rate.

Effect of Ni on growth kinetics, microstructural evolution and crystal structure in the Cu(Ni)–Sn system

Abstract The role of Ni addition in Cu on the growth of intermetallic compounds in the Cu–Sn system is studied based on microstructure, crystal structure and quantitative diffusion analysis. The diffraction pattern analysis of intermetallic compounds indicates that the presence of Ni does not change their crystal structure. However, it strongly affects the microstructural evolution and diffusion rates of components. The growth rate of (Cu,Ni)3Sn decreases without changing the diffusion coefficient because of the increase in growth rate of (Cu,Ni)6Sn5. For 3 at.% or higher Ni addition in Cu, only the (Cu,Ni)6Sn5 phase grows in the interdiffusion zone. The elongated grains of (Cu,Ni)6Sn5 are found when it is grown from (Cu,Ni)3Sn. This indicates that the newly formed intermetallic compound joins with the existing grains of the phase. On the other hand, smaller grains are found when this phase grows directly from Cu in the absence of (Cu,Ni)3Sn indicating the ease of repeated nucleation. Grain size of (Cu,Ni)6Sn5 decreases with further increase in Ni content, which indicates a further reduction of activation barrier for nucleation. The relations for the estimation of relevant diffusion parameters are established considering the diffusion mechanism in the Cu(Ni)–Sn system, which is otherwise impossible in the phases with narrow homogeneity range in a ternary system. The flux of Sn increases, whereas the flux of Cu decreases drastically with the addition of very small amount of Ni, such as 0.5 at.% Ni, in Cu. Analysis of the atomic mechanism of diffusion indicates the contribution from both lattice and grain boundary for the growth of (Cu,Ni)6Sn5 phase.

Solid–state diffusion–controlled growth of the phases in the Au–Sn system

Abstract The solid state diffusion-controlled growth of the phases is studied for the Au–Sn system in the range of room temperature to 200 °C using bulk and electroplated diffusion couples. The number of product phases in the interdiffusion zone decreases with the decrease in annealing temperature. These phases grow with significantly high rates even at the room temperature. The growth rate of the AuSn4 phase is observed to be higher in the case of electroplated diffusion couple because of the relatively small grains and hence high contribution of the grain boundary diffusion when compared to the bulk diffusion couple. The diffraction pattern analysis indicates the same equilibrium crystal structure of the phases in these two types of diffusion couples. The analysis in the AuSn4 phase relating the estimated tracer diffusion coefficients with grain size, crystal structure, the homologous temperature of experiments and the concept of the sublattice diffusion mechanism in the intermetallic compounds indicate that Au diffuses mainly via the grain boundaries, whereas Sn diffuses via both the grain boundaries and the lattice.

Development of different methods and their efficiencies for the estimation of diffusion coefficients following the diffusion couple technique

Abstract The interdiffusion coefficients are estimated either following the Wagners method expressed with respect to the composition (mol or atomic fraction) normalized variable after considering the molar volume variation or the den Broeders method expressed with respect to the concentration (composition divided by the molar volume) normalized variable. On the other hand, the relations for estimation of the intrinsic diffusion coefficients of components as established by van Loo and integrated diffusion coefficients in a phase with narrow homogeneity range as established by Wagner are currently available with respect to the composition normalized variable only. In this study, we have first derived the relation proposed by den Broeder following the line of treatment proposed by Wagner. Further, the relations for estimation of the intrinsic diffusion coefficients of the components and integrated interdiffusion coefficient are established with respect to the concentration normalized variable, which were not available earlier. The veracity of these methods is examined based on the estimation of data in Ni–Pd, Ni–Al and Cu–Sn systems. Our analysis indicates that both the approaches are logically correct and there is small difference in the estimated data in these systems although a higher difference could be found in other systems. The integrated interdiffusion coefficients with respect to the concentration (or concentration normalized variable) can only be estimated considering the ideal molar volume variation. This might be drawback in certain practical systems.