Microstructure characterization, measurement of the coating thickness and WDS X-ray microanalysis were done on TiN and TiC coated Si wafers. Chemical microanalyses were performed using a Leica/Cambridge Stereoscan 440 scanning electron microscope equipped with a Microspec 400 wavelength dispersive spectrometer (WDS). Ti (99.6 wt.%), C (Vitreous) and BN (B = 43.55 wt.% and N = 56.45 wt.%) standards (MAC-Micro Analysis Consultants) were used. Nitrogen quantification was optimized, reducing the influence of the Ti–Ll line (31.36 Å) on the N–Kα line (31.60 Å). Si wafers were used as substrate, so that the WDS microanalyses showed lower peak superposition in the obtained spectra when compared to those obtained for a steel sample.