Extractive Metallurgy Division - Interface and Marker Movements in Diffusion in Solid Solutions of Metals

An experimental study of the movement of markers in the systems Cu/a-brass, Cu/Sna-solid solution, Cu/Ala-solid solution, Cu/Ni, Cu/Au, Ag/Au, employing many types of markers and a variety of temperatures. Marker movement is confirmed and undoubtedly associated with the manner in which atoms move during diffusion. EVERAL years ago Smigelskas and Kirkendall' •S reported measurements on the interdiffusion of copper and a-brass and on the movement of inert markers placed at the original join. These markers were observed to move toward the a-brass side of the join, and from this it was inferred that zinc diffuses in a-brass more rapidly than copper. Similar results were reported a little earlier for the diffusion of solvents into high polymer solids.' This has attracted much attention, particularly from those interested in the mechanism and the theory of diffusion: Seitz3 has employed it in supporting the vacancy theory of diffusion; from the data Darken4 has calculated separate diffusion coefficients for copper and zinc, developing a "phenomenological" theory of diffusion; and Bardeen5 has employed it in constructing a general theory, including therein the work of Seitz and Darken, as has Le Claire. These matters have recently been reconsidered in a sympo~ium.7 Some reason has existed for questioning the work of Smigelskas and Kirkendall.' Their technique consisted in electroplating copper on a-brass, upon the surface of which Mo-wires had been secured, and then diffusing, measuring the extent of diffusion along the normal to the join, and measuring the marker displacement in the same direction by a comparator determination of the distance between Mo-wires on opposite sides of the electroplated brass sample. It has been suspected that the copper plate might have been porous, and that the original interface might have been an imperfect join, both contributing to the transfer of the volatile zinc by vapor transfer;' it has also been questioned whether the marker movement might not in a measure be a property of the marker itself; etc. These legitimate questions require experimental answers; the present paper offers such answers. Moreover, Smigelskas and Kirkendall studied the effect only in the Cu-Zn system and at one temperature; the attention which the work of Smigelskas and Kirkendall has commanded recommends similar