The improved oxidation resistance of TiAlN-based hard coatings is based on the formation of protective oxide scales. Here we report on further improvement of the oxidation resistance of TiAlN coatings by doping with Si and B. An industrial-scale cathodic arc evaporation facility was used to deposit Ti–Al–Si–N and Ti–Al–B–N coatings, with doping contents in the target of up to 2 at.% for Si and 0.5 at.% for B. X-ray diffraction displayed an increased formation of a hexagonal nitride phase for Si and B doped coatings. Oxidation experiments in ambient air showed a decreased thickness of the oxide scale with increasing content of the doping element, where doping with Si was found to be more beneficial than with B. Energy-dispersive X-ray spectroscopy line scans indicated an oxide scale with an Al-rich top-layer and a Ti-rich sub-layer, while Si was homogeneously distributed in both layers. For both doping elements, a modified oxidation sequence of Ti was found, compared to the undoped TiAlN reference coating. In particular, Raman spectroscopy revealed a significantly higher content of the metastable anatase type TiO 2 , at the expense of the stable rutile type TiO 2 , in the formed oxide scale. This is explained by hindered grain growth of the anatase phase followed by a retarded anatase–rutile transformation. Consequently, the time for coarsening of rutile and the accompanied generation of compressive stresses in the Ti-rich sub-layer is reduced. This is responsible for the superior oxidation properties of Si and B doped TiAlN.

Improved oxidation resistance of TiAlN coatings by doping with Si or B

Structure, phase stability and elastic properties in the Ti1–xZrxN thin-film system: Experimental and computational studies

The vacuum cathodic arc deposition (CAD) process is now widely used on an industrial scale to prepare protective hard coatings on cutting tools, metal molds, etc.… It has been recognized that high ionization levels of cathodic arc discharges and high ion energy can provide advantages such as enhanced adhesion required for mechanical applications involving high loads. CAD allows deposition of a wide range of hard compounds as nitrides or carbonitrides. However, CAD is also often associated macrodroplet generation that degrades the surface roughness of coatings. The recent trend is to develop advanced nanostructured hard coatings in order to enhance properties as hardness, toughness, and oxidation resistance. This paper recalls the basic aspects of both CAD technology and nanostructured thin films synthesis. Deposition and characterization of both nanocomposite and nanolayered hard coatings are described. Mechanical behaviors of nitrides can be significantly enhanced by nanolayering. The first example deals with the development of hard nanolayered nitrides coatings for cutting tools protection. It is clearly shown in this example that TiN/AlTiN coatings perform better than CrN/AlTiN and TiN/CrN for the same periods and the best performance is reached for the thinnest periods. It is also shown, in a second example, how silicon addition in CrN can lead to enhancement of oxidation resistance associated with the nanocomposite structure. Thus, relationships are established between deposition conditions, nanostructure and mechanical behaviors or oxidation resistance of the coatings. This short review recalls that CAD remains a powerful and industrial technology for nanostructured hard coatings deposition.

Nanostructured hard coatings deposited by cathodic arc deposition: From concepts to applications

Properties of TiSiN coatings deposited by hybrid HiPIMS and pulsed-DC magnetron co-sputtering

The design of thin hard coatings at a nanometric scale is very promising to improve the surface characteristics of coated parts. Unfortunately, most often only one specific property is really enhanced. Besides, the origin of such a “nanostructure effect” remains still not clearly elucidated, and a wider industrial development requires a better understanding of the relations linking structure and functionality. This paper results from an invited review presented within the framework of the EMRS 2007 spring meeting. Its objective is to present how it is possible to control the films structure to achieve optimized performance in terms of tribological, mechanical, and physico-chemical behaviours. Two types of films architecture are studied, resulting either from a stratification of nanolayers, or from a nanodistribution of a crystallised phase into an amorphous matrix. To illustrate both structures, arc-evaporated nanomultilayered TiN/CrN and TiSiN nanocomposite coatings are more particularly developed, and compared to TiN, CrN and SiN x references. High wear resistance of TiN/CrN is explained by an original propagation mode of the cracks due to a fluctuating residual stress field, evidenced by TEM and synchrotron measurements. Corrosion behaviour depends mainly on the nature of the outer layer. An external CrN layer, presenting a p-type semiconductive character, affords an enhanced protection. A beneficial role of the nanostratification, susceptible to strongly improve the density of films, was also evidenced. The high oxidation resistance of TiSiN is attributable to the network of refractory SiN x , which acts as a diffusion barrier for oxygen and insulates the highly reactive TiN nanograins from the aggressive atmosphere.

Influence of the nanostructuration of PVD hard TiN-based films on the durability of coated steel

Ti–Si–N coatings were deposited on M2 steel by arc evaporation using a Ti–Si composite target in an industrial reactor. The films structure before and after heat treatment at 700 °C was characterised by XRD. In addition, two types of quantitative experiments were performed in thermobalance: oxidation rate was deduced from isothermal thermogravimetric analyses at 800 °C, while the temperature of oxidation beginning ( Tc ) was measured in dynamic mode. Tc was then calculated by a mathematical approximation based on the non-linear least square. The results were compared to those obtained using TiN and SiN x standards. Depending on the deposition conditions, ternary films have been deposited with an atomic ratio Si/Ti of 0.10 and 0.15. The hardness of the films was close to 40 GPa. Only the TiN phase was detected by XRD. The mean crystal size was estimated to be in the 6–8 nm range, which suggested the nanocomposite nature of the coatings. After air oxidation at 700 °C, it was found that this crystal size was not affected by the thermal treatment, indicating a good thermal stability of the structure. Moreover, incorporation of silicon into TiN-based coatings led to a drastic decrease of their oxidation rate, together with a shift of 200 °C of Tc . The high resistance of oxidation of Ti–Si–N films at elevated temperature is attributable to the network of refractory SiN x , which acted as a diffusion barrier for oxygen and insulated TiN nanograins from the aggressive atmosphere.

Oxidation resistance improvement of arc-evaporated TiN hard coatings by silicon addition

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Oxidation resistance improvement of arc-evaporated TiN hard coatings by silicon addition