Interaction of propylamine (PA), 1,2-diaminoethane (DAE) or 3-aminomethyl- 3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA) with native aluminium oxide layers in non-aqueous environment has been studied using time-resolved inductively coupled plasma optical emission spectroscopy (ICPOES) and X-ray photoelectron spectroscopy (XPS). The formation of several surface complexes has been evidenced. Monodentate and bidentate metal-bond surface complexes (MBSC) result from interactions between the amine terminations of the molecule and aluminium cations by donation of the N lone electron pair to the metal ion (Lewis-like mechanism leading to O-Al center dot center dot center dot N bonds). Monodentate and bidentate hydrogen-bond surface complexes (HBSC) are due to interaction of the amino group with surface hydroxyl groups by protonation of the amine termination (Bronsted-like mechanism leading to the formation of Al-OH center dot center dot center dot N bonds) or interaction with carbonaceous contamination (CxOyHz center dot center dot center dot N bonds). Diamines can also form mixed complexes with one amino group forming an O-Al center dot center dot center dot N bond and the other group forming an Al-OH center dot center dot center dot N or CxOyHz center dot center dot center dot N bond. Al-OH center dot center dot center dot N and CxOyHz center dot center dot center dot N bonds are less stable under vacuum than O-Al center dot center dot center dot N bonds, leading to partial desorption of the DAE molecules in vacuum and modi. cation of the interaction modes. Only DAE and IPDA can lead to partial dissolution of the aluminium native (hydr)oxide films. A detailed mechanism of dissolution has been proposed based on the formation of mononuclear bidentate (chelate) MBSC by ligand exchange between the terminal eta(1)-OH and bridged mu 2-OH surface sites and the amino terminations of the molecule. The detachment of this complex from the surface is likely to be the precursor step to the formation of the interphase in epoxy-amine/metal systems. (C) 2008 Elsevier B. V. All rights reserved.