The oxidation of Cu, Zr, and alloys forming chromia, alumina, and zirconia was studied in a closed reaction chamber in O2 gas near 20 mbar. Information on the position of oxide growth has been gained from the 18O/SIMS technique. Rates of O2 dissociation on metal oxides, Au, and Pt have been evaluated from measurements in labeled O2. The experimental results indicate that hydrogen in the metal substrates induces increased metal-ion transport in internal oxide surfaces during oxidation, which leads to increased oxide growth at the oxide–gas interface. Experiments also show that oxides of rare-earth metals (REM) and Pt catalyze the dissociation of O2. An increased rate of O2 dissociation can lead to increased transport of oxygen ions in the oxides and increased oxide growth at the substrate–oxide interface. A balanced transport of metal and oxygen ions in metal oxides that leads to oxide growth at both the metal–oxide and at the oxide–gas interface is found to be favorable for the formation of protective oxides with good adherence to the metal substrate. Depending on the original proporation of metal–to–oxygen ion transport in the oxide, an addition of hydrogen will increase or decrease the oxidation kinetics. In analogy, an addition of REM will increase or decrease the oxidation kinetics, depending on the original proportion of metal-to-oxygen ion transport.
