RI 8378 Electrochemical Corrosion and Film Analysis Studies of Fe and Fe-18Cr in I[N] H2 S04

In this Bureau of Mines investigation, the electrochemical polarization behavior of Fe and Fe-1BCr has been characterized in rigorously controlled 1[N] H2S04 solutions stirred with oxygen or an inert gas. Samples that under-went various levels of corrosion or passivation were examined using Auger electron spectroscopy (AES) and ion sputtering. Passivation of iron occurred at a potential of approximately 0.6 volt (1) in poorly stirred, oxygen-saturated solutions for forward polarization (scanning from cathodic to anodic potentials); (2) in pH-adjusted (increased), well-stirred, oxygen-saturated solutions for forward polarization; and (3) in well~ and poorly stirred, oxygen-and helium-saturated solutions for reverse polarization. Passivation of Fe-18Cr occurred at a potential of approximately -0.1 volt in helium-, nitrogen-, and oxygen-saturated solutions for all cases of forward polarization and most cases of reverse polarization. Elemental depth profiles obtained from AES sputtering measurements indicated that films or adsorbed species were present on iron samples in solution subjected to open-circuit, active, and transpassive corrosion, cathodic reduction, and passivation. This conclusion was reached by considering the distribution of the solution species, primarily sulfur, in the films, which were composed primarily of iron and oxygen. Sulfur was present throughout the films on actively corroding samples, in the outer regions of films of passive and transpassive samples, and on the film surfaces of open-circuit and cathodically reduced samples. For Fe-18Cr, sulfur was found on the surfaces of films on passive samples only, indicating that only the passive samples had films on their surfaces in solution. The films on electropolished and passive Fe-1BCr samples had the largest chromium concentrations, estimated to be approximately 45 at. pct, with less chromium in films of cathodically reduced, active, and open-circuit samples, in that order.