Kinetics of oxide formation in liquid copper and silver

The process of formation of oxide phases in liquid copper and liquid silver has been studied by pumping oxygen into the liquid alloy with the use of a solid-electrolyte electrochemical cell. The oxygen potential at the electrolyte-metal interface is monitored simultaneously by the electrochemical cell. A wide range of effects were observed ranging from the very rapid formation of a layer of oxide at the electrolyte-metal interface to what appears to be homogeneous nucleation of the oxide in the metal. The results may help to explain some of the difficulties that sometimes have been observed in using this type of cell to measure the oxygen potential of a liquid metal. The results indicate that a supersaturation ratio of about 9 is necessary for homogeneous nucleation of iron oxide (most probably Fe₃O₄(s)) in liquid copper containing 0.01 to 0.07 pct iron. The interfacial tensionσ _{Cu-Fe 3}O₄ is calculated to be 0.74 J/m². In experiments with higher concentrations of deoxidant (0.2 pct Fe in Cu and 0.2 to 0.4 pct Ni in Ag) equilibrium precipitation of oxides apparently predominates over homogeneous nucleation for the experimental conditions employed. A mathematical model which partly explains the different effects observed is presented.