Cerium-based conversion coatings are progressing as an effective alternative to hazardous chromate-based systems used in the treatment of metal surfaces. However, there is still considerable debate over the mechanism by which these coatings are formed. Here, titrations of cerium-based conversion coating solutions were carried out in order to model the reactions that occur at the metal-solution interface during coating, with a particular emphasis on investigating the role of hydrogen peroxide (H2O2). The titration curves obtained support the proposed formation of Ce(III) peroxo complexes such as Ce(H2O2)(3+) as an initial step, followed by deprotonation, oxidation and precipitation to form peroxo-containing Ce(IV) species such as Ce-(IV) (O-2)(OH)(2). The precipitates resulting from titrations were characterised by Raman spectroscopy, X-ray diffraction and thermogravimetric analysis, confirming the presence of peroxo bonds, and nano-sized CeO2 crystallites that decreased in size with increasing H2O2 concentration. Characterisation of cerium conversion coatings on aluminium alloy surfaces confirmed the presence of peroxo species in the coatings, thereby supporting the titration model. (c) 2006 Elsevier B.V. All rights reserved.