Scanning ATR-spectroscopy and scanning Kelvin probe studies are introduced as new analysis techniques for the study of water and ion transport at polymer/metal interfaces. The new approach of scanning ATR spectroscopic analysis of water transport at the adhesive/metal interface is combined with scanning measurements in transmission mode of water transport along adhesive joints and non-scanning ATR-measurements of the water transport in a vertical direction through the adhesive. D2O was chosen in some cases instead of water due to its excellent traceability in the infrared spectra. A scanning Kelvin probe was chosen for the detection of the transport kinetics of hydrated alkali ions along the adhesive/metal interface based on the local measurement of interfacial electrode potentials. The complimentary FT-IR techniques showed that the interfacial diffusion of water, in the case of epoxy adhesives on iron, is about two orders of magnitude faster that the transport through the adhesive itself. Similar transport kinetics at the interface is also shown by hydrated ions. Moreover, the here presented FT-IR-ATR and SKP results reveal more information on how adhesion promoting organosilane layers and organosilanes as additives act at polymer/metal interfaces in the presence of water incorporated in the interphase zone. (c) 2005 Elsevier Ltd. All rights reserved.