Institute of Metals Division - Role of Oxide Plasticity in the Oxidation Mechanism of Pure Copper

The mechanism of the oxidation of high-purity copper has been studied at temperatures from 500° to 981°C employing gravimetric, high-temperature microscopic and inert marker techniques. An investigation of the adhesion of copper oxides was also made. The oxidation of copper is found to be parabolic at all temperatures. It is concluded that the controlling mechanism is the outward diffusion of CU+ ions through the Cu2O layer, but the mechanism of diffusion is modified by the state of compressive stress in the oxide layer at the oxidation temperature. At temperatures below the transition from elastic to plastic behavior of Cu2O the growth stresses reach a value sufficiently high to cause CuO whiskers to be extruded. The extrusion of whiskers results in the injection of a large number of vacancies into the CuO. The Cu20 layer grows by the advance of the CuzO/CuO interface into vacancy-rich CuO. Since there is an adequate supply of non -thermally created vacancies, the activation energy for oxidation is that required to move the Cu+ ion through the appropriate saddle point to a neighboring vacancy, which has been determined to be 20,000 cal per mole. At temperatures at which the Cu20 can deform plastically the stresses are never high enough to cause whiskers to form. thus vacancies must be supplied by themal activation and as a result the activation energy increases to 40.000 cal per mole. ALTHOUGH extensive studies of the oxidation kinetics of pure copper have been made in the past. the mechanism has received relatively little attention. As a result, certain features of the kinetic data have not been satisfactorily explained' For example, several workers1,2 have reported that the activation energy for oxidation in the range from 500° to 700° C was about 20,000 cal per mole whereas that above