AA2099-T8 aluminium alloy was anodized at a current density of 5 mA/cm(2) to selected voltages in 0.1 M ammonium pentaborate electrolyte at 293 K. It was found that the growth of barrier-type anodic film on the alloy was accompanied by oxidation of intermetallics, formation and rupture of oxygen gas-filled voids in the anodic film and healing of the anodic film at the sites of rupture. It was revealed that the formation of oxygen gas-filled voids was related to the oxidation of copper-rich nanoparticles in the copper-enriched layer at the film/alloy interface, and that the oxidation process of copper-rich nanoparticles depended on grain orientation. Further, the significantly reduced Pilling-Bedworth ratio for formation of anodic lithium oxide compared with that for formation of anodic alumina resulted in the formation of fine voids at the alloy/film interface and sequentially, detachment of the anodic film from the alloy surface. (C) 2012 Elsevier Ltd. All rights reserved.