HVOF (high velocity oxygen fuel) and multilayer depositions have led to a significant improvement of the film-substrate adhesion due to an increase of the load bearing capacity of the substrate [4–7]. The first work dealing with TiN coatings deposited on plasma nitrided tool steel surfaces was published in the 80s [8] and the plasma nitriding pre-treatments (low and high pressure) became technologically feasible for industrial applications [8–16]. When performed in a hybrid reactor (inside the same chamber), duplex treatments improve the adhesion of the TiN ceramic film to the substrate [13].