Internal-oxide-band formation during oxidation of Ag-Mg alloys

Abstract

Ag-3a/oMg was oxidized in air over the range of 400–900°C. Internal-oxide bands of MgO formed approximately parallel to the surface, the first band appearing at some finite, but irregular depth below the surface. The region between the surface and the first band appeared to be free of precipitates, but TEM showed that very small clusters, about 50 Å in diameter, formed in the “PFZ,” causing significant hardness (greater than 300 VHN). The clusters contain more oxygen than that corresponding to stoichiometric MgO. The hardness between oxide bands was also high, but not as high as in the “PFZ.” The kinetics of thickening of the internal-band region followed the parabolic rate law between 400 and 700° C, with departures from the parabolic law occurring at higher temperatures. The activation energy for the parabolic rate constants was 19.4 Kcal/mol, a value less than the total for oxygen diffusion and oxygen dissolution. The reaction front was planar and parallel to the surface prior to band formation at temperatures of 400–600° C. Nucleation of the first band resulted in nonplanar and nonparallel oxide. Little or no correlation existed between grain boundaries and oxide formation. Nodules of virtually pure silver formed on the surface initially at grain boundaries and subsequently within grains. Nodule formation is attributed to stress-enhanced (resulting from strains associated with precipitation) diffusion of silver to the surface via dislocation pipes. Internal-band formation is discussed in terms of prior data in the literature and various models. It is thought that stress effects (induced by precipitation), nucleation, and clustering of oxygen with Mg play significant roles in causing internal-band formation.