Solidification and Electrolysis of Copper Anodes Containing Nickel, Arsenic, Antimony and Bismuth

In this ?paper practical solidification of anodes containing nickel, arsenic, antimony and bismuth is compared with the equilibrium? diagrams and kinetic ?factors. In order to clarify the distribution of the impurity elements in the anode the structures were studied after the solidification and also after the electrolysis of anodes. This examination was carried out with optical microscope, scanning electron microscope and electrochemical measurements. All the nickel is remaining metallic in the copper matrix during the solidification and therefore nickel is dissolved in the electrolysis at all oxygen contents, when the nickel content is 0.25 wt-% or less in the anode. The practical .solidification mechanism of the anodes, when the nickel content exceeds 0.25 wt-%, proceeds by the crystallization of nickel oxides. In oxygen containing copper anodes nickel oxide is verified to crystallize together with antimony in certain conditions and to form a micaceous compound (3Cu2O?4NiO?Sb2O5), which may build up a very harmful floating slime in the electrolyte. Arsenic is strongly enriched along the phase boundaries in oxygen free copper anodes. An intermetallic compound Cu3As is formed when the amount of arsenic in the anode. exceeds 0.7 wt-%. This compound is more noble than the copper matrix. This means 'that a selective dissolution of copper-arsenic compounds takes place. The copper matrix dissolves more strongly than the grain boundaries. The solidification structures of oxygen free bismuth containing copper anodes show clearly the influence of bismuth. Thin bismuth films which are less .noble than the metallic copper matrix, are formed during the solid1ficatton process. As a result of this the?grain boundaries are dissolved faster than the copper matrix.