Oxidation resistance of decorative (Ti,Mg)N coatings deposited by hybrid cathodic arc evaporation-magnetron sputtering process

Titanium-magnesium nitride coatings (Ti,Mg)N were deposited on steels and silicon substrates by hybrid reactive arc evaporation-magnetron sputtering process from cathodic Ti and sputter Mg targets in an argon/nitrogen gas mixture. X-ray diffraction analyses (XRD) of as-deposited coatings with various Mg/Ti atomic ratios gave evidence of a fcc TiN-like structure strongly oriented in the 111] direction. The TiN lattice parameter increases with the addition of Mg resulting from the substitution of Ti atoms by Mg ones. Optical investigations by spectrophotometry revealed that Mg addition to TiN leads to a change in colour from golden through coppery and violet to grey. Nanoindentation measurements showed that increasing Mg content does not alter the hardness of coatings. As-deposited films were annealed in air from 450 to 750 °C with a 100 °C step. XRD and Raman analyses revealed the formation of rutile TiO₂ and MgTiO₃ phases. Secondary neutral mass spectrometry measurements were performed to study the elemental depth profiles after air annealing. A diffusion of Mg atoms towards the film surface was evidenced above 650 °C, leading to the formation of the MgTiO₃ phase. However, thermogravimetric measurements showed that this oxide phase did not protect the films against high temperature oxidation. On the contrary, below 650 °C Mg affords to TiN a beneficial protective effect, able to reduce the oxidation kinetics by half.