Physical vapor deposition and thermal stability of hard oxide coatings

Abstract: The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite (WC-Co) coated with different combinations of carbide, nitride, and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings, mainly α-Al2O3, are especially desired because of their high hot-hardness, chemical inertness with respect to the workpiece, and their low friction. The search for possible alloy elements, which may facilitate the deposition of such oxides by means of physical vapor deposition (PVD) techniques, has been the goal of this thesis. The sought alloy should form thermodynamically stable or metastable compounds, compatible with the temperature of use in metal cutting application. This thesis deals with process development and coating characterization of such new oxide alloy thin films, focusing on the Al-V-O, Al-Cr-Si-O, and Cr-Zr-O systems.Alloying aluminum oxide with iso-valent vanadium is a candidate for forming the desired alloys. Therefore, coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited with reactive sputter deposition. X-ray diffraction showed three different crystal structures depending on V-metal fraction in the coating: α-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, (63 - 42 at.% V), and a gamma-alumina-like solid solution at lower V-content, (18 and 7 at.%), were observed, the later was shifted to larger d-spacing compared to the pure γ-Al2O3 sample obtained if deposited with only Al-target. Annealing the Al-rich coatings in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 °C for 42 at.% V and 700 °C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure γ-Al2O3-coating which transformed to α-Al2O3 after annealing to 1100° C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The hardness then decreases with increasing V-content, larger than 7 at.% V metal fraction. Doping the Al2O3 coating with 7 at.% V resulted in a significant surface smoothening compared to the binary oxide. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings. This work increases the understanding of this complicated material system with respect to possible phases formed with pulsed DC magnetron sputtering deposition as well as their response to annealing in air.The inherent difficulties of depositing insulating oxide films with PVD, requiring a closed electrical circuit, makes the investigation of process stability an important part of this research. In this context, I investigated the influence of adding small amount of Si in Al-Cr cathode on the coating properties in a pulsed DC industrial cathodic arc system and the plasma characteristics, process parameters, and coating properties in a lab DC cathodic arc system. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating. The effect of Si in the Al-Cr cathode in the industrial cathodic arc system showed slight improvements on the cathode erosion but Si was found in all coatings where Si was added in the cathode. The Si addition promoted the formation of the B1-like metastable cubic oxide phase and the incorporation led to reduced or equal hardness values compared to the corresponding Si-free processes. The DC-arc plasma study on the same material system showed only small improvements in the cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at.% Si in the Al70Cr30-cathode. The presence of volatile SiO species could be confirmed through plasma analysis, but the loss of Si through these species was negligible, since the coating composition matched the cathode composition also under these conditions. The positive effect of added Si on the process stability at the cathode surface, should be weighed against Si incorporation in the coating. This incorporation seems to lead to a reduction in mechanical properties in the as-deposited coatings and promote the formation of a B1-like cubic metastable oxide structure for the (Al,Cr)2O3 oxide. This formation may or may not be beneficial for the final application since literature indicates a slight stabilization of the metastable phase upon Si-incorporation, contrary to the effect of Cr, which stabilizes the α-phase.The thermal stability of alloys for metal cutting application is crucial for their use. Previous studies on another alloy system, Cr-Zr-O, had shown solid solution, for Cr-rich compositions in that material system, in the sought corundum structure. The thermal stability of α-Cr0.28Zr0.10O0.61 coating deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was therefore investigated here after annealing in vacuum up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc-Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. Further in situ synchrotron XRD annealing studies on the α-Cr0.28Zr0.10O0.61 coating in air and in vacuum showed increased stability for the air annealed sample up to at least 975 °C, accompanied with a slight increase in ex-situ measured nanohardness. The onset temperature for formation of tetragonal ZrO2 was similar to that for isothermally vacuum annealing. The synchrotron-vacuum annealed coating again decomposed into bcc-Cr and t-ZrO2, with an addition of monoclinic–ZrO2 due to grain growth. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects present with small grains sizes, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudobinary oxide system also opens up design routes for pseudobinary oxides with tunable microstructural and mechanical properties.