The passive film formed by electrochemical oxidation on two different stainless steels differing in molybdenum (Mo) content in physiological solution with and without the addition of complexing agent, i.e., citrate, was studied using X-ray photoelectron spectroscopy. The alloys were polarized at different oxidation potentials in the electrochemical chamber attached to the spectrometer. Thus, the composition of the film formed by oxidation was analyzed by X-ray photoelectron spectroscopy without prior exposure to air (quasi in situ). The passive film formed in physiological solution consists of two predominant oxides, i.e., chromium and iron oxides. Oxides of alloying elements nickel and Mo are also detected in the film. It seems that the strong enrichment of oxidized chromium and Mo in the passive layer, and strong enrichment of Mo and depletion of iron at the metal surface underneath the passive layer, are responsible for the outstanding corrosion resistance of orthopedic stainless steel in physiological solution. Commercial AISI 304 is not suitable for orthopedic applications. The addition of complexing agent affects significantly the passivation behavior of orthopedic stainless steel, because it changes the distribution of the elements within the passive layer and at the metal surface underneath.
Copyright 2000 John Wiley & Sons, Inc.