Structure and function of ferricyanide in the formation of chromate conversion coatings on aluminum aircraft alloy
Raman and infrared spectroscopy were used to determine the structure of Fe(CN){sup {minus}3}{sub 6} and its reaction products in chromate conversion coatings (CCCs) on AA 2024-T3 aluminum aircraft alloy. In addition, Raman spectroscopy was used to monitor CCC growth rates and their dependence on coating bath composition. The IR and Raman spectra of the air-dried CCC corresponded to those of Berlin green, a Fe{sup +3}-CN-FE{sup +3} polymer, and Fe(CN){sub 6}{sup {minus}3} physisorbed on Cr(OH){sub 3}. No other cyano-containing products were observed. When Fe(CN){sub 6}{sup {minus}3} was excluded from the coating bath, CCC formation rate greatly decreased. In addition, it was observed that Fe(CN){sub 6}{sup {minus}3} could rapidly oxidize AA 2024-T3, and Fe(CN){sub 6}{sup {minus}4} rapidly reduced Cr(VI) in bath conditions. These results indicate a redox mediation action for Fe(CN){sub 6}{sup {minus}3/{minus}4}, which greatly increases the reduction of Cr(VI) to Cr(III) by the alloy. This process is normally quite slow, and redox mediation by Fe(CN){sub 6}{sup {minus}3} is critical to CCC formation. IrCl{sub 6}{sup {minus}3}/{sup {minus}2} could substitute for Fe(CN){sub 6}{sup {minus}3/{minus}4} to produce a chromate film with properties very similar to a conventional CCC. The results establish redox mediation as the mechanism of acceleration of CCC formation, but provide no evidence for any additional role of Fe(CN){sub 6}{sup {minus}3/{minus}4} to produce a chromate film with properties very similar to a conventional CCC. The results establish redox mediation as the mechanism of acceleration of CCC formation, but provide no evidence for any additional role of Fe(CN){sub 6}{sup {minus}3/{minus}4} in corrosion protection.
- Research Organization:
- Ohio State Univ., Columbus, OH (US)
- OSTI ID:
- 20001085
- Journal Information:
- Journal of the Electrochemical Society, Vol. 146, Issue 10; Other Information: PBD: Oct 1999; ISSN 0013-4651
- Country of Publication:
- United States
- Language:
- English
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