Kinetics of formation of fcc-free layers on Co-W-Ti-Ta-Nb-C-N cemented carbides was investigated by experimental methods and DICTRA simulations. The layer formation obeys a parabolic law, indicating a diffusion-controlled process. For DICTRA simulations, the influence of the mobilities for all diffusing elements in the liquid binder phase at the sintering temperature was investigated. The best agreement between experimental and simulations was obtained considering that the mobility of all metallic elements is two times slower compared with the mobility of the non-metallic elements. © 2010 Elsevier Ltd. All rights reserved.