Fw. Lytle et al., AN INVESTIGATION OF THE STRUCTURE AND CHEMISTRY OF A CHROMIUM-CONVERSION SURFACE-LAYER ON ALUMINUM, Corrosion science, 37(3), 1995, pp. 349-369
X-ray absorption spectroscopy (XAS), Fourier transmission infra red sp
ectroscopy (FTIR), X-ray photo-electron spectroscopy (XPS), Auger prof
iling and microscopy were used to characterize chemically and structur
ally the surface oxide layer created by the Alodine 1200S process on 2
024 and 7075 aluminum alloys. The thickness of the layer was found to
range from similar to 2000 Angstrom to 1 mu m for processing times of
1-3 min. The top similar to 20 Angstrom of the fresh Alodine surfaces
were composed of H2O, Cr, Fe and CN. Al and the other elements in the
alloys generally were not components of the top similar to 20 Angstrom
. The Fe and CN were introduced from the Alodine bath and were present
throughout the surface oxide layer as Fe(CN)(6)(3-). The hydration of
the Cr was evident in both the FTIR and XAS spectra. Prior to salt sp
ray exposure the Cr was coordinated with oxygen as similar to 23 +/- 2
% Cr6+ in tetrahedral coordination, Cr-O = 1.71 +/- 0.03 Angstrom, the
balance as Cr3+ in octahedral coordination, Cr-O = 1.99 +/- 0.01 Angs
trom. During salt spray testing similar to 500 Angstrom of the surface
was eroded away and a large fraction of the remaining Cr6+ was chemic
ally reduced to Cr3+ resulting in as little as similar to 7 +/- 1% Cr6
+ in tetrahedral coordination. The other elements in the alloy, i.e. A
l, Cu, Zn, Mn, Ca, Ti and Si were found in the eroded surface. The Cu
and Zn were present and buried within the surface oxide layer essentia
lly in the form of the same intermetallic compounds comprising the ori
ginal bulk alloy. The Alodine process did not change them. The Zn envi
ronment changed slightly during salt spray testing.