# Patent

## Title
Arc evaporated Me11-aMe2aZI/Mo1-b-cSicBbZII multilayer coatings

## Abstract

A coating including a multilayer film, which includes a multi-layered structure including layers of the type I and layers of the type II. The layers of the type I are metal nitride with a chemical composition given by the formula Me11-aMe2aZI and the layers of the type II are a Mo-comprising material with chemical composition given by the formula Mo1-b-cSicBbZII or Mo1-b-cSicBb. Also described is a method for depositing the above mentioned coating.

## Background
The present invention relates to a coating comprising a multilayer film, which is characterized by an multi-layered structure comprising layers of the type I and layers of the type II, wherein the layers of the type I consist of metal nitride with chemical composition given by the formula Me11-aMe2aZI and the layers of the type II consist of a Mo-comprising material with chemical composition given by the formula Mo1-b-cSicBbZII or Mo1-b-cSicBb. The present invention relates furthermore to a method for depositing the above mentioned coating.
BACKGROUND
High temperature oxidation resistance combined with excellent mechanical and tribological properties are typical requirements for state of the art protective coatings.
The growing demands in forming and machining operations, especially in dry machining, typically require further optimizations of well-established coating systems such as TiN, Ti1-xAlxN, and Cr1-xAlxN. Major failure mechanisms in dry high-speed cutting are flank and crater wear, caused through abrasion, adhesion, as well as tribooxidation, and surface fatigue, which all limit the service lifetime of coated tools. Different studies pointed out that such diverse requirement profiles can be controlled through the application of high temperature self-lubricating coatings such as TiAlN/VN, Si3N4—BN, TiC—C, or MoS2.
Solid lubricants are characterized by phases exhibiting easy shear planes, where Magnéli phase oxides (e.g., V2O5, TiO2, and MoO3) are typical examples for high-temperature applications (500 to 1000° C.). Especially, molybdenum is well-known to easily form various Magnéli phases, MonO3n-1, in a wide temperature range starting at 400° C. However, the problem with Mo is the pesting phenomena (i.e., the formation of volatile oxides) leading to an inferior oxidation resistance due to the lack of dense, adherent, and stable oxide scales. Previous studies in the field of high-temperature bulk materials as well as physical vapor deposited coatings highlight that alloying Mo with Si and B results in excellent oxidation resistance as well as thermal stability, even up to 1300° C. The obtained phases, Mo3Si, T1-Mo5Si3, and T2-Mo5SiB2, do not completely inhibit the formation of MoO3, but clearly reduce its volatility. In the low temperature regime, between 650 and 750° C., a slightly porous borosilica scale is formed protecting the underlying material. With increasing temperatures, the borosilica is depleted in B, and the formation of a denser SiO2 scale is promoted. The formation of volatile MoO3 from Mo—Si—B based materials decreases with increasing temperature. Crucial for this behavior is the appropriate phase combination (MoSi3, Mo5Si3, and Mo5SiB2) and chemical composition within the Mo—Si—B system in general. To combine highest oxidation resistance with excellent mechanical properties, the chemical composition of Mo1-x-ySixBy thin films should fulfill the requirement of y/(x+y)≈0.25 with x+y≧0.35. Thereby, hardnesses of 20 GPa and excellent oxidation resistance ( ̃500 nm consumed layer thickness even after 1 h oxidation at 1300° C.) can be obtained. Other molybdenum based systems for enhanced tribological properties are architectural arrangements with MoS2, Mo2N, or MoCN.
WO2014037072A1 discloses coatings containing Mo on tools used for direct hot forming. It is proposed to apply on the tool to a coating system, which contain one or more layer packages comprising a high-temperature-active lubricating layer which with increasing distance from the substrate follows a high-temperature-stabilized layer (called also HT-layer in WO2014037072A1).
Specifically, the coating system according to WO2014037072A1 comprises a layer system made of alternating molybdenum-rich and molybdenum-poor layers, wherein the molybdenum-poor layers are the HT-layers having for example a chemical composition given by the formula (MeWO1, MeWO27 MoWOa)N, and the molybdenum-rich layers are the lubricating layers having for example a chemical composition given by the formula (MeWO3, MeWO4,MoWOb)N, with 0≦WOa<WOb<1 and MeWO1, MeWO2, MeWO3 and MeWO4 being elements selected from Al, Cr, Ti, and preferably MeWO1=MeWO3 and/or MeWO2=MeWO4. WO2014037072A1 teaches furthermore that the molybdenum-rich layers can also comprises one or more elements selected from C, O, Si, V, W, Zr, Cu and Ag for improving lubrication, while the molybdenum-poor layers can also comprises one or more elements selected from Si, W, Zr and B for improving high temperature stability.
Previous studies in the field of PVD processed low friction coatings pointed out the possibilities of architectural designs, such as multilayer or nanocomposite coatings (e.g. TiAlN/VN, TiC—C), to combine particular properties and hence gain superior tribological properties.
SUMMARY
The inventors found that surprisingly particularly good tribological properties can be attained in coatings which have a multilayered structure consisting of Me11-aMe2aZI and Mo1-b-cSieBbZII layers or Me11-aMe2aZI and Mo1-b-cSicBb layers deposited alternating one on each other, when at least the layers of the type I or at least the layers of the type II are deposited by means of arc physical vapour deposition methods. According to a preferably embodiment of the present invention both the layers of the type I and the layers of the type II are deposited by means of arc physical vapour deposition methods.
In the context of the present invention Me1 is one element selected from the group consisting of the groups IVB, VB, and VIIB of the periodic table of the elements except molybdenum. Me2 is one element selected from the group consisting of the group IIIA of the periodic table of the elements and silicon. Mo is molybdenum, Si is silicon, B is boron. Both ZI and ZII can consists of one or more elements selected from the group consisting of carbon (C), oxygen (O) and nitrogen (N) but ZI can be identical or different from ZII. However, as the layers of the type I consist as a metal nitride with chemical composition Me11-aMe2aZI, ZI sloud contain N, it means that ZI can be N or CN or CON. The coefficient “a” corresponds to the concentration of Me2 in the layer of the type I if only Me1 and Me2 are considered for the evaluation of the element concentration. The coefficients “b” and “c” corresponds to the concentration of boron and silicon in the layer of the type II, respectively, if only Mo, Si and B are considered for the evaluation of the element concentration.
According to a further preferred embodiment of a coating according to the present invention particularly good mechanical and tribological properties were attained by depositing inventive coatings comprising layers of the type I consisting of Ti1-aAlaN and layers of the type II consisting of Mo1-b-cSibBc.
According to the present invention the Ti1-aAlaN layers can be deposited by arc evaporation of mixed Ti—Al targets in nitrogen atmosphere. According to the present invention the Mo1-b-cSibBc layers can be deposited by arc evaporation of a mixed Mo—Si—B target (a target comprising Mo, Si and B) or of separated Mo, Si, and B targets. In some cases for example it could be advantageously to use combinations of targets, for example for the deposition of the Mo1-b-cSibBc it could be used a Mo—Si target and a B target or a Mo—B target and a Si target or a Si—B target and a Mo target, or a Mo—Si—B target and a Mo—B target, or 2 or more targets comprising the same elements but in different atomic concentrations.
According to the present invention it is also possible to deposit the Ti1-aAlaN layers by arc evaporation of mixed Ti—Al targets in nitrogen atmosphere and to deposit the Mo1-b-cSibBc layers by sputtering or HIPIMS (HIPIMS=high-power impulse magnetron sputtering) of a mixed Mo—Si—B target (a target comprising Mo, Si and B) or of separated Mo, Si, and B targets. In some cases for example it could be advantageously to use combinations of targets, for example for the deposition of the Mo1-b-cSibBc it could be used a Mo—Si target and a B target or a Mo—B target and a Si target or a Si—B target and a Mo target, or a Mo—Si—B target and a Mo—B target, or 2 or more targets comprising the same elements but in different atomic concentrations.
According to the present invention the coefficients “b” and “c” can vary between 0 and 0.99 atom %.
The combination of Ti1-aAlaN—as a well-established thin film showing high hardness and thermal stability—and Mo1-b-cSibBc—as a Mo based coating system with excellent thermal stability and the ability to form lubricious Magnéli phase oxides such as MonO3n-1—allows attaining excellent wear behavior at elevated temperatures.
According to one more preferred embodiment of the present invention coatings exhibiting a particular high thermal stability and high oxidation resistance can be produced by adjusting the chemical composition of the Mo1-b-cSibBc layers in such a manner that stable borosilica scales can be formed and at the same time the necessary ability for oxidation to form MonO3n-1 Magnéli phase oxides is attained.
For producing and examining some coating according to the present invention, the coating architecture was modified by varying the bilayer period between 4 and 240 nm.
Some individual coating properties, such as hardness, wear rate, coefficient of friction, and thermal stability of the inventive coatings could be correlated with further coating properties which were obtained by detailed transmission electron microscopy examinations.
Ti1-xAlxN is one of the most widely used protective coating systems exhibiting excellent mechanical properties and phase stability at elevated temperatures. The superior mechanical characteristics of Ti1-xAlxN can be attributed to the formation of face-centered-cubic (fcc) TiN and AlN rich domains during the early stages of spinodal decomposition of supersaturated fcc Ti1-xAlxN (leading to age-hardening). The oxidation resistance of Ti1-xAlxN is defined through the Ti to Al ratio, whereas Al-rich coatings are more effective in the formation of alumina rich dense oxide scales.
By combining Ti1-xAlxN with Mo1-x-ySixBy based layers according to the present invention it is possible to produce coatings which exhibit the ability to form lubricious oxide phases (MonO3n-1) integrated with excellent oxidation resistance, which results in outstanding wear and oxidation behavior at elevated temperatures.
Various multilayer combinations, between Ti—Al—N, Mo—Si—B and Mo—Si—B—N, were developed in the context of the present invention and investigated with respect to their growth morphology, mechanical properties, oxidation resistance, and wear performance at temperatures up to 900° C.



BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1a-1d: Cross sectional TEM studies of Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N coatings. Crystalline areas within Mo0.65Si0.15B0.20N are highlighted with solid lines. FIG. 1a shows a cross sectional TEM of a Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer (□=35 nm) exposed to ambient air at 900° C. for 1000 min. FIG. 1b shows a higher magnification of the oxidized area above the droplet-overgrowing multilayer. FIG. 1c shows a TEM-EDS linescan across the oxide scale and Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer (indicated in FIG. 1a by a vertical line).
FIGS. 2a-2d: Cross sectional SEM and TEM images of  ̃0.7 μm thin Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N coatings on top of an arc evaporated Ti0.57Al0.43N adhesion and supporting layer ( ̃1.1 μm).
FIGS. 3a-3d: Cross sectional SEM and BF TEM images of the multilayered Ti0.53Al0.47N/Mo0.54Si0.30B0.16 coating with corresponding SAED pattern and surface topography image on steel substrates. The coating exhibits 6 nm thin Mo0.54Si0.30B0.16 layers and a bilayer period of λ=35 nm.
FIGS. 4a-4d: Cross sectional SEM and BF TEM images of the multilayered Ti0.53Al0.47N/Mo0.68Si0.12B0.20 coating, exhibiting 15 nm thin Mo0.68Si0.12B0.20 layers and a bilayer period of λ=70 nm, with corresponding SAED pattern and surface topography images.
FIG. 5: Hardness and indentation modulus of  ̃0.7 μm thin Mo0.65Si0.15B0.20N and Mo0.68Si0.12B0.20 coatings on top of  ̃1.1 μm Ti0.57Al0.43N adhesion and supporting layers, arc evaporated Ti0.57Al0.43N, as well as Ti0.57Al0.43N/Mo0.54Si0.30B0.16 and Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayers having bilayer periods of λ=35 and 70 nm, respectively.
FIG. 6: Oxide layer thickness in relation to the oxidation time tox=10, 100, and 1000 min for  ̃2.5 μm Ti0.57Al0.43N,  ̃0.70 μm Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N on top of  ̃1.1 μm Ti0.57Al0.43N, as well as Ti0.57Al0.43N/Mo0.54Si0.30B0.16 and Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayers with bilayer periods of λ=35 and 70 nm, respectively. The hatched area on top indicates fully oxidized coatings.
FIG. 7: EDS linescans of polished cross sections of  ̃0.70 μm thin Mo0.68Si0.12B0.20 on top of arc evaporated  ̃1.1 μm Ti0.57Al0.43N after tox=100 min and multilayered Ti0.57Al0.43N/Mo0.54Si0.30B0.16 (λ=35 nm) after tox=1000 min oxidation in ambient air at 900° C.
FIG. 8a: Intact multilayer underneath the protecting oxide scale after 1000 min exposure at 900° C.
FIG. 8b: The intact multilayer and protecting oxide of FIG. 8a at higher magnification.
FIG. 8c: EDS line scans.
FIG. 9a: Coefficients of friction for the materials at different temperatures.
FIG. 9b: Wear rates for the materials at different temperatures.



DETAILED DESCRIPTION
Ti1-xAlxN, Mo1-x-ySixBy, Mo1-x-ySixByN, and multilayered Ti1-xAlxN/Mo1-x-ySixBy coatings were deposited using an industrial coating system of the type INNOVA manufactured by the company Oerlikon Balzers. The coating system was equipped with arc cathodes and sputtering cathodes in order to allow cathodic deposition arc or cathodic sputter deposition or simultaneous cathodic arc/sputter deposition. The targets used as arc cathodes and sputtering cathodes were Ti0.50Al0.50, Mo0.50Si0.30B0.20, and Mo0.625Si0.125B0.25 targets having 99.96% purity, which were produced by using powder-metallurgical techniques by the company Plansee Composite Materials GmbH.
All Ti1-xAlxN coatings and the Ti1-xAlxN layers of the multilayered coating structures were prepared by arc evaporation of the Ti0.50Al0.50 targets using a cathode current of 150 A and a pure nitrogen atmosphere at a constant gas flow of 1000 sccm. Mo1-x-ySixBy and Mo1-x-ySixByN coatings were sputter deposited on an arc evaporated Ti1-xAlxN adhesion and supporting layer. Here, the term homogeneously means that all targets used for the deposition have the same chemical composition and also the other parameters (such as discharge current and gas flow) were constant during the preparation. The Mo1-x-ySixBy coatings and the Mo1-x-ySixBy layers of the multilayered Ti1-xAlxN/Mo1-x-ySixBy coatings were sputter deposited in a pure Ar atmosphere using a flow of 500 sccm and powering the Mo0.50Si0.30B0.20 and Mo0.625Si0.125B0.25 targets with  ̃11 W/cm2. The Mo1-x-ySixByN coating and Mo1-x-ySixByN layer on arc evaporated Ti1-xAlxN were sputter deposited in a mixed N2/Ar atmosphere applying gas flows of N2=400 sccm and Ar=600 sccm, and powering the Mo0.50Si0.30B0.20 and Mo0.625Si0.125B0.25 targets with  ̃11 W/cm2. The arc deposited Ti1-xAlxN adhesion and supporting layers were prepared with a bias potential of −120 V, while for their sputtered Mo1-x-ySixBy and Mo1-x-ySixByN layers a −40 V bias was used. The multilayered Ti1-xAlxN/Mo1-x-ySixBy coatings were prepared by arc evaporation of Ti1-xAlxN in N2 atmosphere with −65 V bias and sputtering of Mo1-x-ySixBy in Ar atmosphere with −40V bias. Their bilayer periods were varied through changing the deposition time of the individual layers. The Ti1-xAlxN/Mo1-x-ySixBy multilayers prepared with the Mo0.50Si0.30B0.20 target exhibits a total coating thickness of  ̃2.80 μm after 80 bilayers. As the sputter rate of the higher Mo-containing Mo0.625Si0.125B0.25 target is nearly twice that of Mo0.50Si0.30B0.20, we also doubled the timer for the individual arc evaporated Ti1-xAlxN layers. Thus, we reduced the numbers of bilayers to 40 to obtain a comparable overall thickness of  ̃2.80 μm. All coatings were deposited on low alloy steel foil (thickness 0.2 mm), polished austenite platelets (20×7×0.8 mm3), Si platelets (100-orientation, 20×7×0.38 mm3), Al2O3 platelets (0001-orientation, 10×10×0.53 mm3), polycrystalline Al2O3 platelets (20×7×0.5 mm3), and polished high speed steel disks (DIN 1.3343-Ø30 mm, thickness 10 mm). Prior to the deposition process the substrates were ultrasonically cleaned in acetone and ethanol for 5 min each, and argon ion etched for 25 min applying the Oerlikon Balzers Central Beam Etching technology (immediately before starting the deposition process within the deposition chamber). The deposition temperature was set to 500° C. and the substrates were rotated using a two-fold rotating carousel.
The structure of the coatings and targets was investigated by X-ray diffraction (XRD) using an Empyrean Panalytical diffractometer (CuKα radiation source) in Bragg Brentano and grazing incidence geometry (incidence angel, Ω=3°).
The oxidation resistance of our coatings (on sapphire substrates), were studied by ambient air annealing in a box furnace at Tox=900° C. for tox=10, 100, and 1000 min. In addition, isothermal oxidation treatments of selected coatings (removing their steel foil substrates with a diluted hydrochloric acid to avoid substrate interference) were performed using differential scanning calorimetry (DSC) combined with thermogravimetric analysis (TGA) at Tox=900 and 1000° C. for tox=300 min. A detailed description of the measurement procedure can be found in R. Hollerweger, H. Riedl, J. Paulitsch, M. Arndt, R. Rachbauer, P. Polcik, et al., Origin of High Temperature Oxidation Resistance of Ti—Al—Ta—N Coatings, (2014). doi:10.1016/j.surfcoat.2014.02.067.
The growth morphology of the coatings was investigated through fracture cross-sections and top view imaging with a FEGSEM Quanta 200 scanning electron microscope (SEM) operated at an acceleration voltage of 15 keV. Selected samples are further studied by cross section transmission electron microscopy (TEM) using a FEI Tecnai F20 field emission TEM operated with an acceleration voltage of 200 kV, and by selected-area electron diffraction (SAED).
The oxidized coatings were chemically analysed by energy dispersive X-ray spectroscopy (EDS) linescans during cross-sectional SEM and TEM studies. SEM-EDS linescans are performed on hot embedded samples (in Struers Poly Fast), which were metallographically prepared with a final 1 μm diamond suspension polishing step. TEM and TEM-EDS line scan investigations are performed on cross-sections prepared with a gallium focused ion beam (FIB, FEI Quanta 200 3D) operated with 5 keV and 0.1 nA for the final polishing step.
The Ti1-xAlxN coatings were chemically investigated by SEM-EDS. To overcome the difficulties in quantification of the boron content, our Mo1-x-ySixBy and Mo1-x-ySixByN coatings were analysed by laser ablation combined with inductive coupled plasma-mass spectroscopy (LA-ICP-MS).
The mechanical properties, hardness (H) and indentation modulus (E), were obtained by analysing the load- and unload-displacement curves of nanoindentation measurements using an Ultra-Micro-Indentation II system (UMIS) equipped with a Berkovich diamond tip after Oliver and Pharr: W. C. Oliver, G. M. Pharr, An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments, J. Mater. Res. 7 (1992) 1564-1583. doi:10.1557/JMR.1992.1564.
Dry sliding tribological investigations were conducted on a standard pin (or ball) on disk testing system (Nanovea) equipped with Al2O3 balls (dball=6 mm) and loaded with 1 N. The coatings, on high speed steel disks, are tested in ambient air with a sliding speed of 0.1 m/s at temperatures of TTribo=RT, 500, and 700° C. and radii of r=11, 8, and 11 mm, respectively. The wear tracks are analysed by chromatographic profilometry (Nanovea).
Morphology and Chemical Composition of the Deposited Coatings:
The chemical composition of the monolithic Mo1-x-ySixBy coatings, sputtered in Ar atmosphere from the Mo0.625Si0.125B0.25 and Mo0.50Si0.30B0.20 targets, correspond to Mo0.68Si0.12B0.20 and Mo0.54Si0.30B0.16. Effects, like gas scattering which are more pronounced for lighter elements, can account for the small loss of boron. The coatings exhibit an amorphous like character as it is shown in the cross sectional TEM images of Mo0.68Si0.12B0.20 with different magnification in the FIGS. 1a and b. The few nm sized, in growth direction slightly elongated grains, are surrounded by a bright appearing tissue phase. Bright field TEM investigations suggest this tissue phase to be enriched in light elements, hence Si and/or B rich. Further studies by, for example, electron energy loss spectroscopy line scans across these tissue phases are needed for more detailed information about their composition and morphology. However, this tissue phase is responsible for renucleation events leading to small grain sizes with an amorphous appearance even during higher magnification TEM studies, which is further suggested by the low intensity continuous SAED ring patterns, FIG. 1b. Sputtering the Mo0.625Si0.125B0.25 target in a mixed Ar/N2 atmosphere leads to the formation of Mo0.65Si0.15B0.20N thin films, with a general columnar, feather-like appearance, FIG. 1c, typical for segregation-driven renucleation. However, compared to the Mo0.68Si0.12B0.20 coating, FIG. 1b, the SAED pattern of Mo0.65Si0.15B0.20N, FIG. 1c, shows diffraction rings from different lattice planes, suggesting for a nano-crystalline structure. Small crystalline areas, with an average size of around 5-10 nm can also be identified by high resolution cross-section TEM investigations, see the areas highlighted with white lines in FIG. 1d. 
Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N coatings were sputter deposited on top of arc evaporated Ti0.57Al0.43N adhesion and supporting layers (to investigate their adherence and crystalline structure) for a better understanding during the preparation of multilayered coatings composed of arc evaporated Ti0.57Al0.43N and sputtered Mo1-x-ySixBy layers. The adhesion between arc evaporated Ti0.57Al0.43N and sputtered Mo0.68Si0.12B0.20 respectively Mo0.65Si0.15B0.20N layers is excellent, FIGS. 2a,b and c,d. The continuing columns across the interface between Ti0.57Al0.43N and Mo0.65Si0.15B0.20N even suggests for partially coherent regions, FIG. 2d. However, glancing angle XRD studies suggest again for an amorphous or nano-crystalline structure of the Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N layer, even when growing them on top of arc evaporated Ti0.57Al0.43N layers. The surface roughness Ra is between 0.038 and 0.056 μm for the Mo0.68Si0.12B0.20/Ti0.57Al0.43N and Mo0.65Si0.15B0.20N/Ti0.57Al0.43N compound coatings.
The multilayered Ti1-xAlxN/Mo1-x-ySixBy coatings, prepared by arc evaporation of Ti0.50Al0.50 targets and sputtering of Mo0.50Si0.30B0.20 targets with 80 bilayers (overall thickness of  ̃2.80 μm), exhibit a very dense featureless fracture cross section, FIG. 3a. TEM cross sections reveal a bilayer period λ of 35 nm composed of 6 nm thin Mo0.54Si0.30B0.16 and 29 nm thin Ti0.57Al0.43N layers, FIG. 3b. The chemical notification of these layers is based on their homogeneously prepared thicker counterparts. The Mo0.54Si0.30B0.16 layers supress the formation of a pronounced columnar growth morphology which would be typical for Ti1-xAlxN coatings leading to the featureless fracture cross section as presented in FIG. 3a. SAED patterns (FIG. 3c) clearly indicate a face-centered-cubic Ti1-xAlxN-based crystalline structure. The higher intensity of the (200) diffraction rings, especially in growth direction, suggests for a predominant 200-growth orientation. (Please note, that the SAED is taken from the cross section, hence the patterns are not along the growth orientation as during plane view investigations.)
The multilayered Ti0.57Al0.43N/Mo1-x-ySixBy coatings prepared by arc evaporation of the Ti0.50Al0.50 targets and sputtering of the Mo0.625Si0.125B0.25 targets, with 40 bilayers to keep the overall coating thickness comparable to the previous multilayer (thickness of  ̃2.80 μm), again exhibit a featureless growth morphology during cross sectional SEM investigations, FIG. 4a. The 70 nm thin bilayer is composed of 55 nm Ti0.57Al0.43N and 15 nm Mo0.68Si0.12B0.20, FIG. 4b. The Mo0.68Si0.12B0.20 layers are clearly thicker as their Mo0.54Si0.30B0.16 counterparts of the previous discussed multilayer, which is mainly based on the higher sputtering rate of the higher Mo-containing Mo0.625Si0.125B0.25 target, please compare FIGS. 3b and 4b. SAED again suggest for a 200 oriented growth, FIG. 4c, with slightly larger grains as compared to the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayers, which is also based on the thicker Ti0.57Al0.43N layers. Nevertheless, the Mo0.68Si0.12B0.20 layers again hinder the development of a pronounced columnar growth morphology and lead to the formation of very dense coatings. Both multilayered coatings, Ti0.57Al0.43N/Mo0.54Si0.30B0.16 and Ti0.57Al0.43N/Mo0.68Si0.12B0.20, have smooth surfaces with roughnesses of about Ra≈0.050 μm, see FIGS. 3d and 4d. 
Mechanical Properties:
The hardnesses of the  ̃0.70 μm thin Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N layers on top of the  ̃1.10 μm thin Ti0.57Al0.43N adhesion and supporting layer are with 15 and 7 GPa, respectively, significantly lower as the 33 GPa of the  ̃2.50 μm thin arc evaporated Ti0.57Al0.43N coating, FIG. 5. Also their indentation moduli are with 280 and 205 GPa lower as the 440 GPa of Ti0.57Al0.43N.
Regardless of the lower hardness and indentation moduli of the Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N layers, the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 and Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayers exhibit H and E values comparable to Ti0.57Al0.43N. Here, the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayers are with 34 GPa slightly harder as the Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayers with 32 GPa. The slightly higher hardness for Ti0.57Al0.43N/Mo0.54Si0.30B0.16 can be based on the smaller bilayer period, 35 vs. 70 nm, and smaller grain sizes, respectively. Probably as the individual Ti0.57Al0.43N layers are still relatively thick with 29 and 55 nm, a superlattice effect was not observed.
Oxidation Resistance:
The oxidation resistance of all coatings investigated is presented in FIG. 6 by the oxide layer thickness after 10, 100, and 1000 min exposure in ambient air at 900° C. The multilayered coatings—orange squares refer to Ti0.57Al0.43N/Mo0.54Si0.30B0.16 with λ=35 nm and red stars to Ti0.57Al0.43N/Mo0.68Si0.12B0.20 with λ=70 nm—clearly outperform all other coatings investigated, exhibiting a consumed layer thickness of only  ̃1.0 μm ( ̃35% of the total coating thickness) even after 1000 min. The almost unchanged oxidized layer thickness with increasing oxidation time from 10 to 1000 min suggests for the formation of a dense oxide scale effectively protecting the coating underneath. Isothermal DSC-TGA measurements (at 900 and 1000° C., not shown here) indicate that the oxidation rate for the multilayer coatings can be best described by a paralinear behavior, w=√{square root over (kp·t)}+c·k1·t [26], where the onset of oxidation is dominated by a parabolic rate to be followed by an extremely low linear rate. The data furthermore suggest for an oxidation activation energy of  ̃97 kJ/mol of the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer. For the other coatings, only the compound coating with a  ̃0.7 μm thin Mo0.68Si0.12B0.20 layer on top of an  ̃1.1 μm thin arc evaporated Ti0.57Al0.43N adhesion and supporting layer (green hexagons) is still intact after 100 min oxidation at 900° C., FIG. 6. Fully oxidized coatings are indicated by the red hatched area in FIG. 6. The arc evaporated Ti0.57Al0.43N coating itself and the compound coating with a  ̃0.7 μm Mo0.65Si0.15B0.20N layer on top of the arc evaporated Ti0.57Al0.43N adhesion and supporting layer (blue diamonds) are already fully oxidized after 100 min at 900° C. This again highlights the oxidation protective behavior of Mo0.68Si0.12B0.20 (but also of Mo0.54Si0.30B0.16, present in the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer with λ=35 nm). Both multilayers have comparable oxidation resistance with a slightly better performance of Ti0.57Al0.43N/Mo0.68Si0.12B0.20 layer (Mo0.54Si0.30B0.16: y/(x+y)=0.35 and x+y=0.46; Mo0.68Si0.12B0.20: y/(x+y)=0.63 and x+y=0.32).
Based on these results the inventors suppose that the required B/Si ratio and minimum Si content to achieve outstanding oxidation resistance will be influenced by other elements present and the coating architecture, such as in our Ti1-xAlxN/Mo1-x-ySixBy multilayers.
EDS line scans on cross-sections of the  ̃0.7 μm Mo0.68Si0.12B0.20 layers (on arc evaporated Ti0.57Al0.43N adhesion and supporting layers) after oxidation in ambient air at 900° C. and tox=100 min, FIG. 7a, indicate by the high oxygen content and Mo-depletion of the outer  ̃1.0 μm—for a fully oxidation of the Mo0.68Si0.12B0.20 layer. The Mo-depletion suggests the formation of volatile Mo-oxides, but also a Mo-diffusion into the entire underlying Ti0.57Al0.43N coating can be detected. The Al-rich zone on top of the oxide scale suggests for the formation of Al2O3, retarding oxygen inward diffusion, although oxygen can also be detected within the arced Ti1-xAlxN layer. Nevertheless, the very high nitrogen signal along the Ti1-xAlxN layer suggests for an intact nitride coating, protected by the outer layer. Increasing the oxidation time to 1000 min leads to a full oxidation of the entire Mo0.68Si0.12B0.20/Ti0.57Al0.43N compound coating.
The Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer with λ=35 nm exhibits a significantly different appearance after the oxidation at 900° C., as suggested by their only  ̃1.15 μm thin oxidized layer thickness, FIG. 6, which can also be identified in the EDS linescan, see FIG. 7b. On top of the coating, the significantly higher signal for Al and oxygen indicate the formation of an Al2O3 outermost scale. This region is depleted in Mo, and followed by a region higher in Ti, lower in oxygen, but significantly depleted in Al. After these zones, oxygen is below the detection limit and the Ti, Al, N, Si, and Mo signals suggest for an intact Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer.
TEM investigations of this Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer, after 1000 min exposure at 900° C., clearly show the intact multilayer underneath the protecting oxide scale, FIG. 8a. 
Especially, the area overgrowing a droplet (indicated by white dashed lines and labelled with droplet) highlights the effectiveness of the Mo0.54Si0.30B0.16 layers to form dense protective oxides. The oxidized area clearly follows the curved nature (due to overgrowing a droplet) of the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer in this region, see FIG. 8a and the higher magnification in FIG. 8b. 
Furthermore, contrary to other arc evaporated or sputtered Ti1-xAlxN coatings, the oxidized area is distinctly separated from the remaining Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer. Our cross section TEM investigations suggest that the Mo0.54Si0.30B0.16 layers—represented by the darker contrast in FIG. 8a—form the border between oxide scale and remaining multilayer. Consequently, the Mo0.54Si0.30B0.16 layers act as barriers for oxygen inward diffusion and retard oxidation kinetics through the formation of dense protective oxides based on borosilica and/or silica. Within the oxide scale, the crystallite sizes significantly increase from the region next to the intact multilayer to the outer surface region. Therefore, distinct SAED diffraction spots are obtained within the outermost oxide scale regions, and continuous ring patterns are obtained near to the multilayer. On the outermost area of the oxide scale, a Si enriched zone can be detected by EDS line scans, FIG. 8c, suggesting the formation of SiO2. Silica seems to be a key requisite in Mo1-x-ySixBy materials to allow for enhanced oxidation resistance above 1000° C. The outermost SiO2 layer is followed by an Al rich zone, Al2O3, and after that by a Ti enriched area, indicative for TiO2. After this sequence, again an Al-rich zone is present, which is followed by a Mo-rich zone, before the line scan as well as the TEM image suggests the intact multilayer.
The layered formation of the oxide scales can be related to the standard enthalpy of formation and the diffusion coefficients of the participating elements. The sequence SiO2/Al2O3/TiO2 would not agree from the sequence in the standard enthalpy of formation, but it is possible, that through the high diffusivity, Si tends to diffuse outwards and forms SiO2 on top, protecting the underlying material. Si also exhibits the smallest atomic radius of 110 μm compared to 140 and 125 for Ti and Al, respectively. Al2O3 is on top of TiO2.
The Mo-enriched oxide zone underneath the SiO2/Al2O3/TiO2, which also exhibits a higher Si content, is an effective diffusion barrier for further oxidation. The dense oxides above the Mo-enriched oxide retard the formation of volatile Mo-oxides, ensuring their effectiveness.
Tribological Behavior:
The coefficient of friction, CoF, for arc evaporated Ti0.57Al0.43N (on high speed steel disks with 65 HRC) is  ̃1.0 at room temperature, the Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayer (with λ=70 nm) as well as the compound layers—with a  ̃0.70 μm thin Mo0.68Si0.12B0.20 or Mo0.65Si0.15B0.20N layer on top of an arc evaporated Ti0.57Al0.43N adhesion and supporting layer—have coefficients of friction of  ̃0.5, FIG. 9a. 
Increasing the temperature from RT to 500 to 700° C. causes a change in CoF for Ti0.57Al0.43N from about 1.0 to 0.5 to 0.6, respectively. The other three coatings (Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayer, Mo0.68Si0.12B0.20/Ti0.57Al0.43N and Mo0.65Si0.15B0.20N/Ti0.57Al0.43N compound coatings) exhibit their highest CoF values (between 0.6 and 1.0) at 500° C., which decreases (to CoF values between 0.4 and 0.6) with increasing Ttribo to 700° C., see FIG. 9a. 
The Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer having a bilayer period of 35 nm exhibits the highest CoF over the whole temperature range among all coatings studied, with rather high values of  ̃2.0 at RT and 500° C. However, at 700° C. the steady state CoF is significantly reduced to  ̃0.7, close to the CoF of the other Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayer having a bilayer period of 70 nm. The relatively high CoF of  ̃2.0 at RT and 500° C. has been cross-checked and confirmed several times also by preparing slightly modified multilayers (with slightly thinner Mo0.54Si0.30B0.16 layers as this Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer with λ=35 nm). Hence, these high values are not an artefact and a result of the multilayer arrangement between arc evaporated Ti0.57Al0.43N and sputtered Mo0.54Si0.30B0.16 layers. However, even these coatings exhibit, especially at RT, lower wear rates as the arc evaporated Ti0.57Al0.43N, see FIG. 9b. The lowest wear rate (≦10−6 mm3/Nm) over the whole temperature range investigated, is obtained for the Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayer having a bilayer period of 70 nm, see the red stars in FIG. 9b. Especially at RT, this multilayer exhibits a by at least two orders of magnitude lower wear rate than the arc evaporated Ti0.57Al0.43N. The low wear rate in combination with the relatively low CoF, especially at RT and 700° C., suggests for excellent tribological properties of the Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayer. Maybe this is based on a complex interplay between Ti- and Mo-based oxides, which can form solid lubricants.
According to the investigation of the deposited Mo0.68Si0.12B0.20/Ti0.57Al0.43N and Mo0.65Si0.15B0.20N/Ti0.57Al0.43N compound coatings—composed of  ̃0.70 μm thin sputtered Mo1-x-ySixBy and Mo1-x-ySixByN layers on  ̃1.10 μm thin arc evaporated Ti0.57Al0.43N layers—and Ti0.57Al0.43N/Mo0.68Si0.12B0.20 and Ti0.57Al0.43N/Mo0.54Si0.30B0.16 multilayer coatings (70 nm bilayer consisting of 15 nm Mo0.68Si0.12B0.20 and 35 nm bilayer consisting of 6 nm Mo0.54Si0.30B0.16) as described above it was determined that:

    
    
        Mo0.68Si0.12B0.20 exhibits an XRD amorphous structure, where nm-sized grains are embedded in a segregation driven tissue phase. Contrary, Mo0.65Si0.15B0.20N shows a columnar, feather-like growth morphology with small  ̃5-nm-sized crystals. Both sputtered layers, Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N, are well adherent to arc evaporated Ti0.57Al0.43N, where even coherent interface regions are formed between Mo0.65Si0.15B0.20N and Ti0.57Al0.43N.
        Although the hardness of the  ̃0.7 μm thin Mo0.68Si0.12B0.20 and Mo0.65Si0.15B0.20N layers on arc evaporated Ti0.57Al0.43N is only 15 and 7 GPa, the Ti0.57Al0.43N/Mo0.54Si0.30B0.16 and Ti0.57Al0.43N/Mo0.68Si0.12B0.20 multilayers exhibit excellent hardnesses of  ̃32-34 GPa and indentation moduli of  ̃385-405 GPa, respectively.
        Ti0.57Al0.43N as well as Mo0.65Si0.15B0.20N/Ti0.57Al0.43N and Mo0.68Si0.12B0.20/Ti0.57Al0.43N compound coatings are already fully oxidized after 100 and 1000 min exposure to ambient air at 900° C., respectively. Contrary, even after 1000 min only  ̃1.05-1.25 μm of the multilayers are transformed into a well adherent and dense protective oxide scale, indicating superior oxidation resistance with respect to their individual components. The oxide scale consists of a layered arrangement of Si-, Al-, Ti-, and again Al-rich oxides above the Mo-rich oxide at the interface to the multilayer.
        Although the mechanical properties as well as the oxidation resistance of both multilayers are comparable and excellent, the Mo-rich multilayer (70 nm bilayer period), Ti0.57Al0.43N/Mo0.68Si0.12B0.20, also show outstanding properties during ball-on-disk tests considering the CoF and wear rates. The steady state coefficients of friction are  ̃0.5 at RT, 500 and 700° C. combined with low wear rates below 10−6 mm3/Nm after 500 m sliding against 6-mm-alumina-balls.
        An optimized architectural arrangement of nm-thin Mo1-x-ySixBy and Ti1-xAlxN leads to superior oxidation resistance (exceeding the oxidation resistance of the individual layers) combined with excellent mechanical and tribological properties.
    
    


Concretely the present inventions discloses a coating comprising a multilayer film exhibiting a multilayered structure formed by a plurality N≧2, preferably N≧4, of layers type I and type II deposited alternated one on each other, unique in:

    
    
        the layers of type I consist of a metal nitride comprising material I having chemical composition Me11-aMe2aZI, and
        the layers of type II consist of a Mo comprising material II having chemical composition

Mo1-b-cSicBbZII or Mo1-b-cSicBb,

where:

        Me1 is one element selected from the groups IVB, VB, and VIIB of the periodic table of the elements excepting Mo, preferably Me1 is Ti,
        Me2 is one element selected from the group IIIA of the periodic table of the elements and Si, preferably Me2 is Al,
        ZI is N or NO or NC or NCO, preferably ZI is N
        ZII is one or more elements selected from N, O and C,
        b and c are atomic concentration coefficients and 1−b−c>0, 0<b≦0.99, and 0<c≦0.99.
    
    


According to a preferred embodiment of a coating according to the present invention:

    
    
        the layers of type I comprise at least mainly and mostly TiAlN or are TiAlN layers, and
        the layers of type II comprise at least mainly and mostly MoSiB or are MoSiB layers.
    
    


According to a further embodiment the layers of the type I and II have individual thicknesses in nanometer magnitude and the bilayer period λ corresponding to the sum of the thickness of one layer of the type I and one layer of the type II deposited one on each other or the sum of the thickness of one layer of the type II and one layer of the type I deposited one on each other in the multilayer film has a value 4 and 240 nm.
Preferably the bilayer period λ is less than 100 nm or less than 50 nm.
Preferably the layers of type I have an individual thickness larger than the layers of type II.
According to one more preferred embodiment of a coating according to the present invention:

    
    
        the layers of type I are TiAlN layers having chemical composition and
        the layers of type II are MoSiB layers having chemical composition Mo1-y-zSiyBz, where:
        
            the coefficients x, y and z correspond to the concentration in atomic percentage of Al in the TiAlN layers without considering the nitrogen concentration,
            the coefficients y and z correspond to the concentrations in atomic percentage of Si and B in the MoSiB layers, respectively,
        
        
        25≦x≦80, 1−y−z>y+z, y>0, and z>0
    
    


Preferably: 1−y−z>50, z<30, and or 1−y−z<80.
The present invention relates at the same time to a method for producing the inventive coatings which comprises the deposition of the layers of the type I by using cathodic arc PVD techniques.
The present invention relates likewise to a method for producing the inventive coatings which comprises the deposition of the layers of the type II by using sputter or HIPIMS PVD techniques.
According to a preferred embodiment of a method according to the present invention the layers of type I are produced by using cathodic arc PVD techniques and the type II are produced by using sputter or HIP IMS PVD techniques.

## Claims

1. Coating comprising a multilayer film exhibiting a multilayered structure formed by a plurality N≧2 of layers type I and type II deposited alternated one on each other, characterized in that:
the layers of type I consist of a metal nitride comprising material I having chemical composition Me11-aMe2aZI, and
the layers of type II consist of a Mo comprising material II having chemical composition


Mo1-b-cSicBbZII or Mo1-b-cSicBb,



where:
Me1 is one element selected from the groups IVB, VB, and VIIB of the periodic table of the elements excepting Mo,
Me2 is one element selected from the group IIIA of the periodic table of the elements and Si,
ZI is N or NO or NC or NCO,
ZII is one or more elements selected from N, O and C,
b and c are atomic concentration coefficients and 1−b−c>0, 0<b≦0.99, and 0<c≦0.99.

2. Coating according to claim 1, characterized in that:
the layers of type I comprise at least mainly and mostly TiAlN or are TiAlN layers, and
the layers of type II comprise at least mainly and mostly MoSiB or are MoSiB layers.

3. Coating according to claim 1 characterized in that the layers of the type I and II have individual thicknesses in nanometer magnitude and the bilayer period λ corresponding to the sum of the thickness of one layer of the type I and one layer of the type II deposited one on each other or the sum of the thickness of one layer of the type II and one layer of the type I deposited one on each other in the multilayer film has a value 4 and 240 nm.

4. Coating according to claim 3 characterized in that the bilayer period λ is less than 100 nm or less than 50 nm.

5. Coating according to claim 1 characterized in that the layers of type I have an individual thickness larger than the layers of type II.

6. Coating according to claim 2, characterized in that:
the layers of type I are TiAlN layers having chemical composition Ti1-xAlxN, and
the layers of type II are MoSiB layers having chemical composition Mo1-y-zSiyBz, where:
the coefficients x, y and z correspond to the concentration in atomic percentage of Al in the TiAlN layers without considering the nitrogen concentration,
the coefficients y and z correspond to the concentrations in atomic percentage of Si and B in the MoSiB layers, respectively,
25≦x≦80, 1−y−z>y+z, y>0, and z>0.

7. Coating according to claim 6, characterized in that 1−y−z>50, z<30.

8. Coating according to claim 6, characterized in that 1−y−z<80.

9. Method for producing a coating according to claim 1 characterized in that the layers of the type I are produced by using cathodic arc PVD techniques.

10. Method for producing a coating according to claim 1 characterized in that the layers of the type II are produced by using sputter or HIPIMS PVD techniques.

11. Method according to claim 9, wherein the layers of type I are produced by using cathodic arc PVD techniques and the type II are produced by using sputter or HIPIMS PVD techniques.

12. Coating according to claim 1 wherein the multilayer structure is formed by N≧4 of the layers type I and type II.

13. Coating according to claim 1 wherein Me1 is Ti, Me2 is Al, and ZI is N.