Institute of Metals Division - Crystal Structures and Transformations in Indium-Thallium Solid Solutions

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with