W/WCNx coatings were produced by using a repetitive pulsed vacuum arc discharge on stainless-steel 304 substrates, varying the substrate temperature from room temperature to 200 degrees C. Energy dispersive spectroscopy (EDS) was used for determining W, C and N concentrations dependence on the substrate temperature. A competition between C and N can be observed. Atomic force microscopy was employed for obtaining the thickness and grain size that present similar tendencies as a function of the temperature. X-ray diffraction characterization showed phases of W and alpha-WCN (hexagonal). Raman spectra for all substrate temperatures were obtained, presenting two peaks corresponding to D (disorder) and G (graphite) bands in the region of 1100-1700 cm(-1) due to the amorphous carbon. As an important conclusion, it was stated that substrate temperature has strong influence on the structure, chemical composition and morphology of W/WCNx bilayers, caused by the competition between carbon and nitrogen. (C) 2012 Elsevier B. V. All rights reserved.