A better understanding of the composition and structure of chemically treated Al alloy surfaces is necessary to devise new, more environmentally benign, coating systems for aircraft. In this work, the surface of AA2024-T3, as well as analogs for constituent intermetallic compounds (IMC), were examined at various stages of the Al alloy pretreatment and chromate conversion coating (CCC) process. A complement of techniques were used: imaging and dyanmic Secondary Ion Mass Spectroscopy (SIMS), Variable-Angle X-ray Photoelectron Spectroscopy (VA/XPS), Synchrotron Infrared Microspectroscopy (SIRS), X-ray Absorption Spectroscopy (XAS), and Electrochemical Impedance Spectroscopy (EIS).; The water and hydrocarbons in commercial CCC destabilized Cr(VI) during exposure to soft x-rays. However, it was possible to prevent photochemical reduction with the ultra-clean vacuum pumping practice recently developed at Stony Brook. The type of pretreatment used prior to chromate conversion coating influenced the extent of IMC removal, Cu (re)distribution, and surface activity. Cu(I) was observed on all the chemically treated surfaces. Samples pretreated in Sanchem 1000 while galvanically coupled to a Pt mesh had a more desirable distribution of Cu for subsequent processing. Chromate reduction was not a significant factor in CCC aging over a 24-hr period, but surface dehydration and structural change were correlated and causative. Imaging SIMS revealed heterogeneities in the CCC that varied laterally with IMC in the alloy substrate. These regions were depleted in compounds containing Cr, F, and CN. Cu was found at localized sites in the CCC contact surface. Cyano groups were bound as Cr(IlI)-CNFe(H). The chromate available for CCC repair was located on matrix regions through the entire bulk of the CCC. The presence of residual contaminants (e.g. cleaning agents, metal working fluid, ink) affected the distribution of activator compounds (e.g. ferricyanide) in a CCC. The cyanide complex (Cr(Ill)-Fe-CN6) was found in the CCC bulk not just at the outermost surface. A new model for CCC on Al-Cr alloys is proposed. The model is based on the sol-gel-like nascent CCC that limits the transport of IMC dissolution products.
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