Zr-based conversion film fabricated on cold rolled steel by separately providing zirconium and fluorine ions: Performance and mechanism study

Abstract

Controlling the concentrations of Zr4+ and F− in traditional Zirconium (Zr)-based film-formation solution is challenging due to their dependence on the hydrolytic equilibrium of H2ZrF6. In this study, Zr-based films were prepared on cold rolled steel surface through the film-formation solution prepared by mixing Zr(NO3)4 and different amount of HF. The electrochemical results demonstrated that the Zr-based film prepared by Zr(NO3)4 and HF exhibited superior corrosion resistance compared to H2ZrF6. Under optimal film formation conditions, the protective efficiency of the prepared film reached 74.4 % which was higher than that of film fabricated in H2ZrF6. The electrochemical results concurrently demonstrated the self-reinforcing anti-corrosion performance of the prepared films. Scanning electron microscopy revealed that the Zr film, prepared in Zr(NO3)4 and HF, exhibited excellent corrosion resistance attributed to its high film density. The X-ray photoelectron spectroscopy and energy dispersive spectroscopic results indicated the presence of a fluoride layer on the surface of the Zr film. The F− ions can chelate with the corrosion products and selectively deposit onto the damaged areas of the film, thereby effectively contributing to the repair of the film layer. The results of density functional theory calculations demonstrated that Zr4+ readily forms Zr(OH)4 rather than ZrF62−. The present study offers an enhanced approach for regulating the properties of films prepared via H2ZrF6 by separately providing zirconium and fluorine ions.