Technical Notes - Embrittling Effect of Molybdenum on Electrodeposited Copper

IN the course of small seale experiments on the electrodeposition, of copper, extremely brittle deposits were obtained from electrolytes prepared by leaching calcined chalcopyrite with aqueous sulfuric acid. It was not possible to strip the metal without fracture after it had been deposited from such electrolytes onto smooth oiled copper sheets, the usual plant procedure for the production of so-called starting sheets. The embrittlement did not occur with electrolytes made either by leaching the calcine with water or by treating an acid leachate to remove iron as hydrous ferric oxide. The electrolytes which produced brittle deposits were found to contain molybdenum in concentrations of 10 to 25 mg per 1, whereas those which produced ductile deposits contained <0.5 mg per 1. Synthetic electrolytes having the composition: Cu", 40 gpl; Fe", 0.5 to 1.0 gpl; Fe3+, 0.5 to 1.0 gpl; and H,SO,, 10 to 50 gpl, were prepared from reagent-grade salts; by adding ammonium molybdate, the embrittling effect of the higher concentrations of molybdenum (VI) was strikingly confirmed. The brittle deposits contained up to 0.03 pct Mo. The importance of oxidation state of the molybdenum was demonstrated when the electrolyte containing it was circulated continuously through a bed of fine copper metal during deposi- tion. Under these reducing conditions, the cathode deposit was ductile and molybdenum could not be detected. Molybdenum has not been recognized as one of the metals causing embrittlement of copper nor is it listed among the usual impurities. In most elec-trowinning plants there is a purification step which removes iron from the leachate before electrolysis. In these cases molybdenum would be coprecipitated with hydrous ferric oxide. In the case of the large leaching plant at Chuquicamata, Chile, where the leachate is reported to contain considerable molybdenum, it would be reduced to a lower oxidation state during removal of chlorine by means of cement copper. This may explain why the embrittling effect of molybdenum has not been reported previously. Moreover, in copper refining plants where soluble anodes have been prepared by a high temperature smelting process, it is most unlikely that any molybdenum would remain with the copper, whereas the calcines in this work were prepared in a fluidized bed reactor at a temperature not exceeding 720°C. Acknowledgment This work is part of an investigation on the roasting and extraction of copper from sulfide ores sponsored jointly by Mt. Morgan Ltd., Queensland, and the Mt. Lyell Mining and Railway Co. Ltd., Tasmania.