Florian Frank

As the demands for wear-resistant coatings in the cutting industry are constantly rising, new materials that have the potential to exhibit enhanced coating properties are continuously explored. Chemical vapor deposited (CVD) Zr(N,C) is a promising alternative to the well-established and thoroughly investigated Ti(C,N) coating system, owing to its advantageous mechanical and thermal properties. Thus, within this work, CVD ZrN, ZrCN and ZrC coatings were deposited at 1000 °C, and subsequently their microstructure and mechanical properties were investigated in detail. Scanning electron microscopy, electron backscatter diffraction and X-ray diffraction experiments revealed that all coatings exhibited a columnar structure and a fiber texture, where ZrN and ZrCN displayed a preferred orientation in growth direction and ZrC showed a texture. Tensile residual stresses that arise due to a mismatch in the coefficient of thermal expansion between the cemented carbide substrate and the coating material decreased with the addition of C to the coatings. No stress relaxation through thermal crack formation was observed in the coatings. The highest hardness was determined for the ZrC coating with 28.1 ± 1.0 GPa and the lowest for the ZrN coating with 22.1 ± 0.9 GPa. Addition of C to the ZrN coating increased the hardness to 26.1 ± 1.6 GPa, which can be explained by a more covalent bonding character, as well as by solid solution strengthening. The ZrCN coating exhibited the highest Young’s modulus, followed by the ZrC and ZrN coatings, which can be attributed to differences in their electronic band structure.

The oxidation behaviour of chemical vapour deposited ZrN, ZrC and ZrCN coatings was investigated using in-situ synchrotron X-ray diffraction (XRD). To obtain a precise analysis of the temperature–dependent phase evolution during oxidation, coating powders were annealed in air between 100 °C and 1000 °C. Simultaneously, 2D XRD patterns were recorded in ~2 °C increments, which were subsequently evaluated using parametric Rietveld refinement. The results were correlated with differential scanning calorimetry and thermogravimetric analysis measurements, to further illuminate the oxidation mechanism of each coating system. ZrCN exhibited the highest oxidation onset temperature, followed by ZrC and ZrN. Furthermore, ZrCN was completely oxidised at a temperature of ~720 °C, which was ~50–70 °C higher than for ZrN and ZrC. The in-situ experiments revealed a similar oxidation sequence for all three samples: first, tetragonal and/or cubic (c/t)–ZrO₂ is formed, which subsequently transforms into the more stable monoclinic (m)–ZrO₂ phase. ZrCN and ZrC showed a higher c/t–ZrO₂ fraction than the ZrN sample at 1000 °C. Furthermore, ex-situ Raman and XRD investigations of the oxidised samples revealed the ongoing c/t–ZrO₂ → m–ZrO₂ phase transformation during cooling.