The mechanical durability of seven commercially polymeric coatings is investigated using slow positron beam techniques to monitor changes in sub-nanometer defects during the process of cyclic loading. Doppler broadened energy spectra and positron annihilation lifetime (PAL) measurements were performed as a function of the slow positron energy at different periods of cycling loading. The positron annihilation dada show that both S-defect parameter and o-positronium (Ps) lifetime decrease as the loading cycle increases. The results indicate a loss of free volumes due to the loss of mechanical durability by cyclic loading. A direct correlation between the loss of S-defect parameter and the period of loading cycle is observed. This is interpreted as that durability of polymeric coatings is controlled by the atomic level free volumes. It is shown that the slow positron beam is a very successful probe in detecting the very early stages of coating degradation due to mechanical processes. (C) 2002 Elsevier Science B.V. All rights reserved.