The Effect of Microstructure on the Electrochemical Behavior of Lead-Silver Alloy Anodes during Zinc Electrowinning

During the casting of lead-silver anodes, variations in cooling rates result in the formation of an uneven microstructure. The slowly cooled areas (SCA) have a coarser microstructure than that of the remaining part (called "the general zone"). The effect of anode microstructure on the electrochemical behavior was investigated using galvanostatic, potentiodynamic and electrochemical impedance techniques. The results show that the resistances for the two steps of the oxygen evolution reaction on the slowly cooled areas of Pb- Ag anodes are higher than that on the general zone. The double layer capacitance for the first step of the oxygen evolution reaction (OER) and the pseudocapacitance of the second step of OER on SCA are smaller than those on the general zone. The potentiodynamic results show that the amount of lead dioxide formed on the SCA is greater than that of the general zone of the anode. The potential decay curves after 30 minutes of galvanostatic polarization at 45 mA/cm2 show that the corrosion potential of the SCA is 200 mV lower than that of the general zone. This can lead to perforation because of the formation of a galvanic cell with a small anode and a large cathode.