Recent Advances in Understanding Passivity of Metals and Alloys Philippe Marcus Institut de Recherche de Chimie Paris/ Physical Chemistry of Surfaces CNRS-Chimie ParisTech Ecole Nationale Supérieure de Chimie de Paris 11 rue Pierre et Marie Curie, 75005 Paris, France philippe.marcus@chimie-paristech.fr Recent advances in the understanding of passivity of metals and alloys at the nanoscale will be presented, in which passivity and initiation of localized corrosion were investigated using advanced surface analytical techniques such as STM, STS, XPS,ToF-SIMS, combined with electrochemical measurements, and complemented by DFT modelling. The following points will be addressed : The metal/water interface : interrogating the early stage of interaction (using in situ Scanning Tunneling Microscopy (STM)) Nanostructure of passive oxide films on metals (Cu, Ni, Cr) and alloys (stainless steels): - Crystallinity of passive films : evidence of the crystalline nature of passive films on several metals (Cu, Ni, Cr) and alloys (ferritic and austenitic stainless steels) - Oxide/metal epitaxy : the epitaxial relationship between inner oxide films and metallic substrates - Effects of time of polarization on oxide crystallinity - Compositional heterogeneity of surface oxides on stainless steel Effect of surface defects on localized corrosion studied at high resolution Atomistic modelling of corrosion using density functional theory (DFT)