Low-temperature oxidation is a reaction, occurring at or below room temperature, between a solid and a gas. It usually involves the combination of oxygen with metals, and it has the greatest commercial impact in the presence of moisture, as in corrosion. Cabrera and Mott put forward a theory of low-temperature oxidation, based on the assumption that cation migration occurs under the influence of a potential built up across the growing oxide film. Recent experimental results require that this theory be expanded to explain recent observations such as anion migration during oxide growth and the transition from the initial chemisorbed monolayer to a bulk, threedimensional oxide. The additional ideas put forward in the present paper may be summarized as follows. Low-temperature oxidation is controlled by the nature of the oxide; whether it is a network former or a modifier. A period of fast, linear oxidation is followed by a slow logarithmic reaction whose rate, in turn, can increase if the oxide film crystallizes to form grain boundaries. The initial fast oxidation is a continuation of the chemisorption process. Place exchange (anions and cations interchanging positions) occurs when the energy due to the image force of an oxygen ion is greater than the bond energy holding the ion in place. A stable film forms when this bond energy is greater than the image force energy. The oxygen ions formed on the oxide surface then set up a potential across the film. This potential provides the driving force for continued reaction. Oxide growth during this later stage is a slow, logarithmic process. A barrier to ion transport exists at the gas-oxide interface in the case of anion migration and at the metal-oxide interface in the case of cation migration. In both cases, the field built up across the oxide lowers the barrier sufficiently so that ion migration can occur. Network modifiers allow cation migration. The reaction rate is sensitive to crystallographic orientation of the metal, but not to oxygen pressure. A constant voltage is maintained across the film, so that the Cabrera-Mott theory explains the logarithmic kinetics. Network-forming oxides allow onion migration. The number of anions, and hence, the rate of reaction, is sensitive to oxygen pressure, but not crystallographic orientation of the metal substrate. Since the potential is a result of the mobile anions, the film tends to grow under constant field. The logarithmic kinetics then must be explained by an increasing activation energy for ion transport, as proposed by Eley and Wilkinson. The logarithmic growth rate can be increased by the presence of water vapor if the water introduces “dangling” bonds into an oxide network structure. Crystallization of the oxide film also increases its rate of growth and results in the formation of oxide islands.

Low-temperature oxidation

The formation kinetics and electric properties of anodic barrier oxides on Al, Hf, Nb, Ta, Ti, and Zr depend on the migration of ions, controlled by an electric field strength of up to 107 V cm−1. The high field model, based on ideas of Guntherschulze, Betz, Verwey, Mott, and Cabrera, explains only parts of the experiments. Contradictory models and investigations of the last 60 years are compared with new results, which enable a more detailed understanding of many aspects of the high field model, e.g. the shape of experimental transients, the time and field dependent concentration of mobile ions, the nature of the mobile species and the interaction of anion and cation transport, and the location of the rate determining step.

Thin anodic oxide layers on aluminium and other valve metals: high field regime

A detailed review of the principles governing the oxidation of metals is presented. It covers the initial stages of oxidation, oxide film formation, thick film and scale formation and oxide structure.

https://iopscience.iop.org/article/10.1088/0034-4885/37/2/002/pdf

The oxidation of metals

Anodic Oxide Films

The reaction of O2 with Al(1 1 0): a medium energy ion scattering study of nano-scale oxidation

Capacitance measurements have been used to distinguish between the effective field and ionic avalanche models for the autocatalytic buildup of ionic current on applying a constant high field to tantalum pentoxide films.

C. J. Dell'Oca

Papers

Mechanism of ionic conduction at high fields