Electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments

In reinforced concrete, a passive layer forms because of the alkaline conditions in the pores of the cement paste, where large concentrations of hydroxides create a solution with pH typically between 12 and 14. The corrosion resistance of the material depends on the characteristics and integrity of the passive film; however, currently very limited information is available about the passive films formed on carbon steel under such conditions. This work presents an electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments. More specifically, the study focuses on the characterization of the films formed on ASTM A36 steel reinforcing bar exposed to aqueous solutions that aim to reproduce the chemistry of the environment typically found within the cement paste. Electrochemical techniques such as cyclic potentiodynamic polarization curves, galvanostatic cathodic polarization and linear polarization resistance were employed, in addition to in-situ Surface Enhanced Raman Spectroscopy (SERS). The experimental setup was built in a way that SERS experiments could be performed simultaneously with potentiodynamic polarization curves, enabling a detailed analysis of the formation and reduction of the surface films as a function of applied potential. Three solutions with different pH levels were used for the polarization and SERS experiments, namely 0.55M KOH + 0.16M NaOH ([OH-]=0.71), 0.08M KOH + 0.02M NaOH ([OH-]=0.10) and 0.008M KOH + 0.002M NaOH ([OH-]=0.01). Additional NaOH solutions in which the pH was varied from 13 to 9 and the ionic strength from 10 -5 to 10-1 were prepared for a pilot study using linear polarization resistance.;Results show that the features observed in the cyclic potentiodynamic polarization curves correlated well with the potential arrests observed in the GCP plots as well as with the changes observed in the SERS spectra, providing valuable information about the formation of passive films on carbon steel in each of the environments studied in this research. Although there are key differences among the films formed in the different solutions tested---particularly regarding their thickness and protectiveness---once the film-formation processes had been completed, generally the films were characterized by an inner layer of Fe(II) and an outer layer of Fe(III). A Fe(OH)2-like species appears consistently as dominating the inner Fe(II) layer, while the outer typically composed mostly by gamma-Fe2O3 and/or gamma-FeOOH. Film thickness varied from about 22 nm to 266 nm depending on the pH of the solution, and decreased as pH was reduced.