Institute of Metals Division - The Uranium-Silicon Epsilon Phase

RECENTLY, a description of the wartime work in this laboratory on the U-Si phase diagram was published. This diagram was available earlier in the open literature; as were Zachariasen's crystal structure identifications for the compounds in the system. The uranium end of the phase diagram is shown in Fig. 1. The most recent work on this system has emphasized the peritectoid E phase, of particular interest for a number of reasons. The early work provided evidence of this phase's resistance to corrosion in water and of its slight ductility. Further information on these properties has been obtained here. Work elsewhere4 has provided evidence of stability under irradiation. This body-centered-tetragonal phase is relatively isotropic compared to the more usually applied a or ? uranium phases. Unlike the other compounds in this system, it contains no Si-Si covalent bonds.3 In addition, consideration on the basis of Pauling's concepts leads to the conclusion that in the E phase, uranium has a higher valence than in any of the other phases. Definition of the composition of the ? phase has been of prime concern in the study of this alloy. Evidence is presented below that its silicon content is slightly higher than that of stoichiometric U8Si, the composition frequently assigned this phase on the basis of Zachariasen's identification. This work on the composition required careful attention to the method of dissolving the alloy for analysis, since apparently low silicon contents could be found under certain conditions, see Appendix. Preparation: Melting, Casting, and Heat Treatment—Almost all the samples were from castings with a diameter of 13/4 or 2 in. and about 1 ft long, weighing 10 to 15 lb. The U-Si charge was melted by heating to about 1650°C in an induction heated vacuum furnace. Beryllia crucibles were used at first, but were replaced by zirconia-washed graphite as the technique of keeping the carbon content low enough (about 500 ppm) was mastered. The alloy was bottom-poured at about 1650°C into graphite molds. A few small buttons, weighing no more than 50 g, were prepared in a small arc melting unit.' Since cast material has a preponderance of uranium and U8Si2, heat treatment is necessary to ob-tain the ? phase by the solid-solid peritectoid reaetion. Once obtained, the ? phase is stable to room temperature, obviating the need for speeial attention to the method of cooling after epsilonization, see Fig. 1. It was found desirable to epsilonize at 800°C for a week. For some purposes, in which residual uranium and/or U8Si2 are tolerable, shorter periods may be adequate. The temperature of 800°C is not critical, since essentially the same results were obtained from 785° to 825°C. Further departure from this epsilonization range is inadvisable.