Extractive Metallurgy Division - Production of Malleable Zirconium on a Pilot-Plant Scale

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made