Alloys calciothermic reduction

An estimate of world calcium consumption in 1986 indicated that lead refining uses 30% alloys, eg, with Pb, Al, and Si, 25% steel treatment, 20% calciothermic reduction, 10% calcium hydride, 10% and miscellaneous usage is 5%. More recent evidence, however, has suggested that increasing consumption of calcium in battery manufacture has made this the most significant use. 

In many instances of commercial importance an alloy, rather than a metal, is obtained as the product of calciothermic reduction. The alloy may be an intermediate in metal preparation or even the end product of the process. 

Calciothermic reduction of samarium oxide, in the presence of cobalt powder, yields samarium-cobalt alloys in the powder form. The process is popularly known as reduction diffusion. Samarium oxide, mixed with cobalt powder and calcium hydride powder or calcium particles, is heated at 1200 °C under 1 atm hydrogen pressure to produce the alloys. Cobalt oxide sometimes partly replaces the cobalt metal in the charge for alloy preparation. This presents no difficulty because calcium can easily reduce cobalt oxide. A pelletized mixture of oxides of samarium and cobalt, cobalt and calcium, with the components taken in stoichiometric quantities, is heated at 1100-1200 °C in vacuum for 2 to 3 h. This process is called coreduction. In reduction diffusion as well as in coreduction, the metals samarium and/or cobalt form by reduction rather quickly but they need time to form the alloy by diffusion, which warrants holding the charge at the reaction temperature for 4 to 5 h. The yield of alloy in these processes ranges from 97 to 99%. Reduction diffusion is the method by which most of the 500 to 600 t of the magnetic samarium-cobalt alloy (SmCOs) are produced every year. 

Several other useful modifications of calciothermic reduction have been successfully developed for the preparation of this neodymium-bearing magnetic alloy. One of these is reduction-extraction which involves the reduction of neodymium sesquioxide (Nd203) with calcium in a molten calcium chloride-sodium chloride salt bath at 750 °C and the simultaneous extraction of the reduced metal into a molten neodymium-zinc or neodymium-iron alloy pool. The neodymium-zinc alloy product is treated in vacuum to remove zinc and produce neodymium metal, while the neodymium-iron alloy is itself the end product of... 

Fig. 26. Process outline for the production of rare earth-transition metal magnet alloy powders by calciothermic reduction and solid-state diffusion. R/D is reduction-diffusion, and KOR is Koreduktion...

One of the important differences between calciothermic and aluminothermic reduction of oxides concerns the interaction between the reduced metal and the reductant. Calcium does not form stable solid solutions or alloys with the reduced metals calcium contamination in the metal is, therefore, relatively small. Aluminum, on the other hand, readily forms solid solutions with the reduced metals, and the product generally contains appreciable quantities of residual aluminum. This is not a serious problem because in many cases either a certain aluminum content is desired in the reduced metal or the residual aluminum can be effectively removed in post-reduction purification operations. The extent of the contamination of a reduced metal with the reductant can be related to factors such as the reaction temperature, the standard free energy change associated with the reaction, and the slag composition. Let the following generalized reaction be considered ... 

The R-Fe-B alloys may be prepared by reducing with calcium, at high temperature, the respective rare-earth oxides, in the presence of a mixture of transition metals in powder form plus some transition metal oxides (Herget 1985a). Two versions of calciothermic processes for making rare-earth alloys were proposed the reduction-diffusion (R-D) process (Cech 1974, McFarland 1973) and the co-reduction process (Herget and Domazer 1975, Domazer and Strnat 1976). The last one consists of a simultaneous reduction of rare-earth and transition metal oxides in the presence of transition metal powder, followed by diffusional alloys formation. The process may be divided into two steps ... 

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