Diffusion of iron in Cr2O3:: polycrystals and thin films

Chromia protective layers are formed on many industrial alloys to prevent corrosion by oxidation. The role of such layers is to limit the inward diffusion of oxygen and the outward diffusion of cations. A number of chromia-forming alloys contain iron as a major component, such as the stainless steels. To check if chromia is a barrier to the outward diffusion of iron in these alloys, iron diffusion in chromia was studied in both polycrystals and oxide films formed by oxidation of Ni-30Cr alloy in the temperature range 700-1100 degreesC at an oxygen pressure equal to 10(-4) atm. An iron film of about 80 nm thick was deposited on the chromia surface, and after the diffusing treatment, iron depth profiles were established by secondary ion mass spectrometry (SIMS). Two diffusion domains appear whatever the nature of the chromia material, polycrystals or films. In the first domain, using a solution of the Fick's second law for diffusion from a thick film, effective or bulk diffusion coefficients were determined. With the second domain, Le Claire's and Hart's models allowed both the bulk diffusion coefficient and the grain-boundary diffusion parameter (alphaD(gb)delta) to be obtained. Iron bulk and grain-boundary diffusion does not vary significantly according to the microstructure of chromia. The activation energy of grain-boundary diffusion is at least equal or even greater than the activation energy of bulk diffusion, probably on account of segregation phenomena. Iron diffusion was compared to cationic self-diffusion in the bulk and along grain boundaries and related to the protective character of chromia. (C) 2004 Elsevier B.V. All rights reserved.