Ag surface diffusion and out-of-bulk segregation in CrN-Ag nano-composite coatings

CrN-Ag nanocomposite coatings are deposited on Si(100) wafers and 20MnCr5 steel disks in a mixed Ar+N2 atmosphere by reactive magnetron sputtering. Structure, composition and morphology were investigated by Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES), X-ray Photoemission Spectroscopy (XPS), X-ray Diffraction (XRD) and Focused Ion Beam (FIB) cross sectional analysis. The as deposited film matrix is mainly composed by CrN phase (78%), but a relevant part (28%) is composed by Cr2N. Ag agglomerates in the CrN matrix forming elongated grains 200-400 nm wide and 50-100 nm high, which extends on the top of CrN columns. At the surface Ag aggregates into two different structures: large tetrahedral crystalline clusters, with typical dimension ranging from 200 to 500 nm, and smaller Ag nanoparticles with diameter of 15-25 nm. The annealing in N2 atmosphere up to 500 degrees C does not affect size and distribution of the Ag grains in the sub-surface region, while it induces a size increase of the bigger Ag clusters on the surface, mainly related to Ag surface diffusion and clusters coalescence. Annealing at higher temperature leads to an evident Ag out-of-bulk segregation, generating Ag depleted voids in the near-surface region, and further increasing of the Ag clusters size at the surface. Tribological tests on as deposited CrN-Ag film reveal a coefficient of friction against a steel ball reduced with respect to CrN film, probably related to the presence of Ag which acts as solid lubricant, but the coating is removed after a very short sliding distance. The poor mechanical properties of the realized Ag-based coatings are confirmed by lower hardness and Young modulus values with respect to pure CrN.