The growth of barrier-type anodic films at high efficiency on a range of sputtering-deposited Al-Hf alloys, containing from 1 to 95 at.% Hf. has been investigated in ammonium pentaborate electrolyte. The alloys encompassed nanocrystalline and amorphous structures, the latter being produced for alloys containing from 26 to 61 at.% Hf. Except at the highest hafnium content, the films were amorphous and contained units of HfO2 and Al2O3 distributed relatively uniformly through the film thickness. Boron species were confined to outer regions of the films. The boron distributions suggest that the cation transport number decreases progressively with increasing hafnium concentration in the films, from similar to 0.4 in anodic alumina to similar to 0.2 for a film on an Al-61 at.% Hf alloy. The distributions of Al3+ and Hf4+ ions in the films indicate their similar migration rates, which correlates with the similarity of the energies of Al3+ -O2- and Hf4+ -O2- bonds. For an alloy containing similar to 95 at.% Hf. the film was largely nanocrystalline, with a thin layer of amorphous oxide, of non-uniform thickness, at the film surface. The formation ratios for the films on the alloys changed approximately in proportion to the hafnium content of the films between the values for anodic alumina and anodic hafnia, similar to 1.2 and 1.8 nm V-1 respectively. (c) 2008 Elsevier Ltd. All rights reserved.