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The aim of this work was a comparative investigation of the structure and properties of Al- and Cr-doped TiSiCN coatings deposited by magnetron sputtering of composite TiAlSiCN and TiCrSiCN targets produced by self-propagating high-temperature synthesis method. Based on X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy data, the Al- and Cr-doped TiSiCN coatings possessed nanocomposite structures (Ti,Al)(C,N)/a-(Si,C) and (Ti,Cr)(C,N)/a-SiCxNy/a-C with cubic crystallites embedded in an amorphous matrix. To evaluate the thermal stability and oxidation resistance, the coatings were annealed either in vacuum at 1000, 1100, 1200, and 1300°C or in air at 1000°C for 1h. The results obtained show that the hardness of the Al-doped TiSiCN coatings increased from 41 to 46GPa, reaching maximum at 1000°C, and then slightly decreased to 38GPa at 1300°C. The Cr-doped TiSiCN coatings demonstrated high thermal stability up to 1100°C with hardness above 34GPa. Although both Al- and Cr-doped TiSiCN coatings possessed improved oxidation resistance up to 1000°C, the TiAlSiCN coatings were more oxidation resistant than their TiCrSiCN counterparts. The TiCrSiCN coatings showed better tribological characteristics both at 25 and 700°C and superior cutting performance compared with the TiAlSiCN coatings. © 2011 Elsevier B.V.

Nanocomposite coatings combining hard phases (TiB2, TiC) with amorphous carbon (a-C) were developed to provide a good compromise between mechanical and tribological properties for M2 steels used in a wide variety of applications such as cutting tools, bearings and gear mechanisms. A combined d.c.-pulsed and r.f.-magnetron deposition process was used to deposit nanocomposite TiBC/a-C coatings with a variable content of carbon matrix phase. Chemical composition was determined by electron energy-loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS). Transmission electron microscopy (TEM) revealed that the coatings microstructure is rather amorphous with small nanocrystals of TiC and/or TiB2 (not possible to differentiate by diffraction techniques). Investigation of the chemical bonding environment by XPS and EELS allows us to confirm the presence of titanium-boron and titanium-carbon bonds together with free amorphous carbon. Coatings exhibited hardness values (H) of 25–29 GPa, effective Young modulus (E*) of 310-350 GPa, H/E* ratios over 0.080 and resistance to plastic deformation (H3/E*2) from 0.15 to 0.20. Tribological properties of the coatings were characterized by a pin-on-disk tribometer using steel and WC balls at high contact stresses (1.1 and 1.4 GPa respectively). Friction coefficients were reduced from 0.6 to 0.2 by increasing the content of free carbon without reduction of the hardness (around 28 GPa), by self-lubricant effects. The tribomechanical data are revised according to the phase composition and chemical bonding inside the nanocomposites.