AbstractThe objective of the research reported in this paper was to refine an existing model for chromate conversion coatings (CCC) formed on the surface of AA2024‐T3, an Al–Cu aircraft alloy, by considering the composition and structure of the CCC formed on constituent intermetallic compounds (IMCs). To achieve this aim it was necessary to develop large‐area samples composed of compositionally homogeneous thin films of the various IMCs found on the AA2024‐T3 surface, which were galvanically attached to thin films of Al–4.2wt.%Cu (representative of the AA2024‐T3 matrix). This was performed in a two‐step process: disks of IMC compositions were formed by reactive arc melting (RAM), followed by femtosecond laser ablation of the RAM IMCs, resulting in the formation of homogeneous thin films. These thin films were used to analyze the formation of CCC on IMCs, the AA2024‐T3 matrix analog and matrix–IMC galvanic couples. Secondary ion mass spectrometry depth profiling revealed significant variations in CCC film thickness and composition related to the underlying IMCs. The SIMS results indicated that the CCC formed on the matrix analog had the same average thickness as the average CCC formed on AA2024‐T3, whereas those formed on individual θ and S phases were only 9% and 12% as thick, respectively, when uncoupled to the matrix and 11% and 14% as thick when coupled to the matrix. The CCC thickness on the Al20Cu2(MnFe)3 was found to be variable, having an islanded structure. Topographical maps indicate that the IMC/matrix boundaries are covered with CCC of a thickness approaching that of the matrix. Inhibition of CCC growth is related to the high copper content (and therefore insufficient aluminum) present in the IMCs compared to the matrix, which provides a more accurate model of CCC formation on AA2024‐T3. Copyright © 2002 John Wiley & Sons, Ltd.