Dehydration-Induced Loss of Corrosion Protection Properties in Chromate Conversion Coatings on Aluminum Alloy 2024-T3

It is well known that chromate conversion coatings (CCCs) exhibit a prompt loss in corrosion resistance when exposed to moderately elevated temperatures (60-100°C). They also suffer a gradual loss in corrosion resistance due to ambient temperature exposure. To better understand the origins of losses in corrosion resistance, CCCs were formed on 99.99% Al, 1100 Al [Al-1.0(Fe, Si, Cu)], and 2024-T3 (Al-4.4Cu-1.5Mg-0.6Mn), exposed to elevated and ambient temperature exposures for various lengths of time, and characterized using several different methods. The Cr(VI):total Cr ratio in CCCs was estimated by analysis of data derived from X-ray absorption spectroscopy. Corrosion resistance was measured by electrochemical impedance spectroscopy. The evolution of shrinkage cracking was examined by environmental scanning electron microscopy. Cr(VI) leaching experiments were also carried out to characterize the effect of thermal exposure on Cr(VI) release. Thermal analysis and X-ray diffraction were conducted to characterize the temperature-dependent changes in CCCs. Results show that CCCs degrade in several distinct steps over the temperature range of 20 to 500°C. Our findings support the longstanding notion that dehydration is the root cause for losses in corrosion resistance due to aging at ambient and low temperatures (<150°C). Extended X-ray fine structure measurements indicate a shortening in Cr(III)-Cr(III) nearest neighbor distances upon dehydration. This is interpreted as a consolidation in the Cr(OH)_3 backbone of the CCC which leads to shrinkage cracking and immobilization of Cr(VI). This finding is important because it links older observations of the effects of aging and heating on CCCs to newer interpretations of CCC formation based on inorganic polymerization. Overall, these results reveal CCCs to be highly dynamic coatings with corrosion resistance properties that vary considerably in both the short term and long term

Formation of Chromate Conversion Coatings on Aluminum and Its Alloys

In situ X-ray adsorption near-edge structure (XANES) has been used to investigate the formation of chromate conversion coatings on pure Al, commercial Al alloys (AA 1100, AA2024, and AA7075), and a series of binary Al–Cu alloys. The method employed cells designed to determine the growth of the total chromium [Cr(total)] and hexavalent chromate [Cr(VI)] in the chromate conversion coating (CCC) as a function of exposure time to a chromate solution. Three sets of data were obtained, where (i) the Al was exposed to only a limited amount of solution; (ii) the chromate solution was excluded after short periods of repeated exposures to the solution; and (iii) the Al was exposed continuously to the chromate solution. All the results showed a very rapid initial growth within the first seconds, followed by a continued increase in thickness for exposures up to 1 h. Measurements with Al–Cu binary alloys demonstrated that the difference observed in AA2024 and AA1100 may not be due to Cu alloying. The proportion of Cr(VI) in the coatings becomes approximately constant after 180 s of exposure for all the specimens examined, even though the coatings continued to grow

The effect of chromate concentration on the repassivation of corroding aluminum

Current density maps of anodically polarized pure aluminum in chloride solutions were measured and the effect of chromate/dichromate buffer additions monitored. The higher the polarized potential the more chromate was required to repassivate the corroding surface. Small pits repassivated easily, crevice corrosion events were the last to repassivate. Open circuit potential measurements showed the presence of meta-stable pitting at chloride concentrations of 0.3M. The lifetime and magnitude of these metastable pits was reduced on the addition of 0.05M chromate buffer