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The kinetics of and mechanism for galvanising low-carbon steel (0.2% C) were examined in powder media which were pre-treated to obtain a fine nanostructured ZnO layer on the surface of zinc powder particles. The effective diffusion coefficient of Zn atoms through the ZnO shell was estimated to be in the order of 1·10−10 m2·s−1. The contribution of the Zn-gas evaporation/condensation microprocesses, which could occur in relation to the above diffusion through a nanostructured surface layer, was evaluated with numerical calculations in the temperature range of 550–950 K and for an average particle size of ZnO up to 100 nm. Our results suggest that the outward diffusion of metallic zinc takes place from the core of powder microparticles across the nano-grain boundaries of their modified surface layer, and can be further intensified by the presence of other inter-phase defects, such as nano-porosity.