Zirconium exhibited pseudo-passive behavior in fluorinated nitric acid (11.5 M HNO3 + 0.05 M NaF) as the current density measured from the electrochemical studies was several orders higher than the value in fluoride free nitric acid. Impedance studies on zirconium sample exposed in 11.5 M HNO3 for 240 h confirmed the formation of the passive film with high polarization resistance value and the calculated thickness of the film based on the capacitance value was about ~4.5 nm. On the other hand, in fluorinated nitric acid, the charge transfer resistance value associated with the zirconium dissolution process was dominant when compared to that of the film formation. Results of X-ray photoelectron spectroscopic investigations upheld the presence of ZrOF2 and ZrF4 and indicated that the protective oxide layer growth was restricted by the presence of fluoride ions.
Titanium (Ti) is a lustrous transition metal which possesses excellent corrosion resistance in several aggressive environments but is attacked by acidic fluoride media. In this work, the addition of fluoride ion to nitric acid on the corrosion behavior of Ti and air-oxidized Ti was studied. Air oxidation of Ti at 800 °C for 5 h resulted in the formation of an intact rutile TiO2 layer with a thickness of about 35 μm. The corrosion resistance was investigated from the polarization resistance ($$R_{\text{P}}$$RP) values which were obtained from linear polarization and electrochemical impedance spectroscopy (EIS) measurements. A decrease in the $$R_{\text{P}}$$RPvalue of Ti with the addition of fluoride ion in nitric acid was observed, and this indicated the formation of an unstable layer, which resulted in accelerated dissolution. The several order increase in the $$R_{\text{P}}$$RPvalue of air-oxidized Ti in nitric acid containing fluoride ions pointed the improved resistance to corrosion. The diffusivity of species through the air-oxidized TiO2 layer was estimated from the electrochemical equivalent circuit (EEC) analysis of EIS data. Even though the diffusivity increased by several orders with the addition of fluoride ions, air-oxidized Ti provided better protection against nitric acid containing fluoride ions than Ti. The corrosion rates of Ti and air-oxidized Ti in boiling nitric acid containing fluoride ions were also estimated from weight loss experiments. Even in boiling fluorinated nitric acid, air-oxidized Ti provided better corrosion protection, with corrosion rates of about 1000 times less than that of Ti.