PART IV - Diffusion in the Disordered Cadmium-Magnesium Solid Solution

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do's or the H'S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.' In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,' the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.' Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.' The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.'' Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule