BRPI0719774B1 - Layered system with at least one mixed crystal layer of a polyoxide, and part for use at high temperatures and / or high chemical loading. - Google Patents

Description

(54) Title: LAYER SYSTEM WITH AT LEAST ONE MIXED POLYOXIDE CRYSTAL LAYER, AND PIECE FOR EMPLOYMENT AT HIGH TEMPERATURES AND / OR HIGH CHEMICAL LOAD (73) Holder: OERLIKON SURFACE SOLUTIONS AG., TRÜBBACH. Address: Hauptstrasse 53, CH-9477 Trübbach, SWITZERLAND (CH) (72) Inventor: JÜRGEN RAMM; BENO WIDRIG; MICHAEL ANTE; CHRISTIAN WOHLRAB

Validity Term: 10 (ten) years from 10/02/2018, subject to legal conditions

Issued on: 10/02/2018

Digitally signed by:

Liane Elizabeth Caldeira Lage

Director of Patents, Computer Programs and Topographies of Integrated Circuits

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Invention Patent Report for SYSTEM IN LAYERS WITH AT LEAST ONE MIXED CRYSTAL LAYER OF A POLYOXIDE, AND PIECE FOR EMPLOYMENT AT HIGH TEMPERATURES AND / OR HIGH CHEMICAL LOAD.

[001] The present invention relates to a system of coating layers obtained by physical vapor deposition for the coating of work tools according to the generic term of claim 1, as well as a process for preparing a respective coating system. layers, according to the general term of claims 21 and 26. In addition, the invention relates to work tools, according to the generic term of claim 42, which are coated with the layer system, according to the invention . State of the art [002] EP 0513662 and US 5 310 607 (Balzers) describes a layer of rigid material of (Al, 0) 2 () 3, a coated tool, and a process for preparing the layer, in which Al and Cr powders are evaporated together from a crucible connected as an anode to the discharge of a low voltage arc (NVB), and tools are coated at about 500 ° C in an Ar / 02 atmosphere. The layer has internal compression stresses and consists essentially of mixed crystals with a Cr content greater than 5%, with thermodynamic stability being enhanced by a high aluminum content, resistance to abrasive wear is enhanced by a high content of chrome. The layer is designated as a modification of α-aluminum oxide (corundum), by means of a supposed Line 202 that presents a corresponding shift with the chromium content, however in these evaluations all other corundum lines are missing. Despite the mentioned advantages, these layers could not be established as an industrial standard, since the preparation with the NVB process already described, due to the insulating properties of the bedsPetition 870180031782, of 04/19/2018, p. 5/17

2/36 of, in continuous operation, leads to technical processing problems.

[003] An outline of these technical process problems, by precipitation of a layer at least sufficiently conductive of a tertiary nitride and a subsequent oxidation step, is described in the following three documents. All three documents, however, aim to make available an oxide layer or deposits in the corundum structure, such as substrates for the growth of an α-aluminum oxide layer. The latter is prepared by means of an unbalanced spray with Magnetron (Unbalanced-Magnetron-Sputtering) (UBMS) in an atmosphere of Ar / O ₂ with expensive process supervision through a plasma emission monitor (PEM), to keep Al spray targets in a transition strip between a contaminated, therefore oxidized and metallic surface.

[004] US 6 767 627 and JP - No. 2002-53946 (Kobe) describes a layer system and a method for preparing a layer system containing α-aluminum oxide. Thus, for example, a rigid layer of TiAIN and an AlCrN are applied, for example, then at least the surface of the rigid layer of AlCrN is oxidized, resulting in a lattice structure with a crystalline constant between 0 , 4779 and 0.5 nm as an intermediate layer. The layer of α-aluminum oxide is precipitated on it (a = 0.47587 nm). The authors state that they can prepare layers in a corundum structure also at temperatures between 300 and 500 ° C, by means of an AIP process with the following oxidation step, and then aluminum oxide UBMS. Alternatively, aluminum oxide layers that were precipitated in CR ₂ O ₃ , (Al, Cr) ₂ O ₃ or intermediate layers of (Fe.Cr) ₂ O _{3 are} also disclosed, also with UBMS in an Ar / O ₂ atmosphere. In addition, the authors mention,

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3/36 with respect to JP 5-208326, the poor suitability of the intermediate layers of (Al, Cr) ₂ O ₃ or (Fe, Cr) ₂ O ₃ for the processing of steels, based on the chromium reaction on the surface of layer with the iron of the material to be worked.

[005] Comparatively, the inventors of these same claimants recognize in the most recent US 2005 005 00850 (Kobe) that these techniques actually require temperatures from 650 de to 800Ό, since at lower temperatures oxidation does not occur. In fact, only examples are disclosed at a temperature of 700 and 750 ° C and a method in which at least the oxidation step or precipitation of the aluminum oxide film occurs at a temperature of 700 ° C and above. It is preferred that both process steps are carried out at the same temperature. In addition, the inventors disclose the additional introduction of a diffusion barrier containing Ti, such as TiN, TiC, TiCN among others, to prevent harmful diffusion of oxygen through the oxide layer that occurs at these high process temperatures.

[006] WO 2004 097 062 (Kobe) also provides for the need for improvement in the invention described in JP-N ° 2002-53946. The starting point is, therefore, a test in which JP N ° 2002 53946 CrN is oxidized at 750 ° C, and then aluminum oxide is precipitated at the same temperature through a spray-controlled process PEM in an atmosphere of Ar / O ₂ . This leads to thicknesses of increasing and crystalline layers, however with increasing thickness, rough grains are always formed, and therefore too rough layers. To assist the WO 2004 097 062 test through a process in which the crystal growth of aluminum oxide, or is interrupted in periodic time periods by thin oxide layers of other metal oxides equally increasing in the corundum structure, such as Cr ₂ O ₃ , Fe ₂ O ₃ , (AICr) ₂ O ₃ ,

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4/36 (AIFe) ₂ O3, or at least by periodic deposits of such oxides. Thus the strips of layers that cover the other metal oxides should be kept below 10, preferably even below 2%. The long coating times for preparing such layers, from about 5 hours to 2 pm, however seem to be unsuitable for industrial processes.

[007] An Ashenford publication [Surface and Coatings Technology 116-119 (1999) 699-704] describes the growth of aluminum oxide in the corundum structure and chromium oxide in the schoolite structure in the temperature range between 300 ° C and 500 ° C. The school structure of chromium oxide is the same as the corundum structure of aluminum oxide, however it has a slightly modified network parameter. The objective of the tests carried out with an MBE system in UHV was to use chromium oxide in the corundum structure as a crystallization substrate for the growth of the high temperature corundum phase of aluminum oxide. The oxygen is thus stimulated by the plasma, the metals separated from elementary sources are evaporated, and locally they are so arranged that the material flow reaches the substrate at the same time. Amorphous aluminum oxide can be precipitated on steel substrates in the observed temperature range between 300 and 500 ° C, whereas chromium oxide, largely independent of the pretreatment of steel substrates, can grow as a polycrystalline layer in the structure of schooling. Pure α-aluminum oxide, however, also cannot be prepared on the layers of scholarite, since in this temperature range from a concentration greater than 35% of aluminum atoms the crystal structure within some atomic locations is converts to amorphous aluminum oxide. This practical observation was subsequently confirmed by simulation calculations using a semi-empirical model, which provides for a destabilization of the oxide

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5/36 of α-aluminum by locations of locations lacking oxygen in favor of the k modification.

[008] EP 0 744 473 B1 describes a spraying process, which substrate temperatures below 700 ° C, leads to a layer consisting of the α and γ phases of aluminum oxide, which is totally crystalline, however it presents, at high compression stresses, at least 1 GPa. As intermediate layers between the tool and the aluminum oxide layer, metallic compounds with O, N and C are mentioned.

[009] In summary it can be said that the state of the art, in the field of preparing oxides in the corundum structure by means of physical vapor deposition processes, has been striving for well over 10 years to prepare layers of α oxide -aluminum, to be able to offer an equivalent to a layer in the CVD range of very successful for a long time, without the disadvantages caused by the CVD process. The processes are so complex, error-prone and complicated that today, only one manufacturer has offered an amorphous layer of aluminum oxide, however no crystalline and particularly no layer of α-aluminum oxide in the field of aluminum coating. tools. For reasons similar to today, no other particularly thick oxide layer was offered, although among others the offer of oxy-nitrides, oxycarbonitrides and the like shows that in the tool market there is a great need for thermodynamically resistant coatings. Definitions [0010] By being thermally stable in the sense of the present invention, layers are understood, which in an air temperature range ranging from room temperature to at least 900 ° C, preferably 1000 ° C, and particularly 1100 ° C, do not present no modification to the crystal structure and, therefore, no essential modificationPetition 870180015576, of 02/27/2018, pg. 11/54

6/36 in the X-ray diffractogram, and consequently in the network parameter. Such layers, provided that they have a corresponding basic hardness of at least 1500 HV, preferably at least 1800 HV for use in tools with high thermal demand, are particularly interesting, since no phase change process is expected during the step processing and thermal hardness vis-à-vis other layers is noticeably better. [0011] Stress-free can be understood as the layers that present, with the verification process here described in more detail below, the lowest compressive and tensile stresses. With this, for example, one can directly infer the Al content, respectively the Cr content, of the layer through the linear interpolation between the crystal constants of the binary compounds of a-AI ₂ O ₃ and a-Cr ₂ O ₃ , from the deviation of the spacing of the crystal network planes or the crystal constants of the (AICr) ₂ O ₃ layers (Vegard's Law).

[0012] This occurs in contrast to the physical vapor deposition process known from EP 0513662 and EP 0744473. The layers described there, which due to the introduction of noble gas atoms, direct current bias or for other reasons, grow tense, present increasing internal compressive stresses in the range above a GPa, which often lead to ruptures for the largest layer thicknesses.

[0013] CVD layers, on the other hand, usually show tensile stresses, usual due to the different thermal expansion coefficients of the layer and the base material during cooling from the high precipitation temperatures typical of the process. For example, for precipitation of a-AI ₂ O ₃ according to US 2004202877, temperatures between 950 and 1050 ° C are required. This, with the additional disadvantage of an inevitable content of deposit products 870180015576, of 02/27/2018, p. 12/54

7/36 undesired composition (for example, halogens) of the precipitation process, is the main disadvantage of the CVD coating process, since these stresses lead to the formation of cracks, for example crest cracks and therefore the layers for the processes for example, they are inappropriate for interrupted cutting.

[0014] Here are called polyoxides, the compounds of at least two or more metals with an oxide. In addition, oxides of one or more metals can also be included, which additionally include one or more semiconductor elements, such as, for example B or Si. An example of such oxides are the cubic aluminum dioxides or polyoxides known as spinel. However, the present invention relates to oxides, which have an isomorphic α-aluminum oxide of the corundum type of the composition (Me1i. _X Me2 _x ) ₂ O ₃ , in which Me1 and Me2 respectively cover at least one of the elements Al, Cr , Fe, Li, Mg, Mn, Ti, Sb or V, and thus the elements Me1 and Me2 are different respectively.

Measurement methods [0015] Below are briefly mentioned some methods and devices for characterizing certain layer properties for the purpose of better comparison.

X-ray diffraction measurements [0016] For measurements of XRD spectra and network constants calculated from them, a Bruker D8 X-ray diffractometer - AXS with GÃõbel mirror, Soller slit and dispersive energy detector was used.

[0017] The simple measurement of Θ-2Θ occurred in BraggBrentano geometry with Cu-ka radiation, band incidence.

[0018] The angular range of 20 to 90 °, with rotating substrate.

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8/36 [0019] Measurement time: at a residence time of 4 s at 0.01 ° the measurement time was 7 h 46 min (for 70 ° C).

Measurement of the internal stresses of the layers [0020] For the measurements of the internal stresses of the layers, on the one hand, the method of flexing the strips according to Stoney on hard metal rods (L = 2r - 20 mm, D _s = 0, 5 mm, E _s = 210 GPa, v _s = 0.29) and the layer tension was calculated according to the following formula:

E, * D?

* L ² * d _f with E _s ... Young modulus of the substrate, D _s ... total thickness of the substrate, d _f ... layer thickness, f ... flexion and f ... free length of stem.

[0021] On the other hand, the method of flexing disks used and the tension of the layers was calculated according to the following formula:

(1-vJ 6 * I ² d _f with L = 2r = 20 mm, D _s = 0.5 mm, E _s = 210 GPa, y _s = 0.29 [0022] Additionally the deviation found between the measurement points of a polyoxide, measured by X-ray diffraction, and the line determined by Vegard's law, gives information about the internal stresses in the layered compound.

Overview [0023] It is the task of the present invention to perfect the disadvantages of the prior art described in detail above, and to provide a layer system suitable for use at high temperatures that contains at least one thermally stable oxide layer, as well as a part , particularly tools and construction parts, which are protected by the layer system. Another task is to offer a process for preparing the

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9/36 layer system, which makes it possible to reproduce parts in a simple and safe way and adjust the properties of the layer system for different jobs.

[0024] The task is solved by a system of coating layers obtained by physical vapor deposition for the coating of parts, which at least covers a mixed crystal layer of a polyoxide of the following composition:

(Me1i. _X Me2 _x ) ₂ O ₃ [0025] Since Me1 and Me2 respectively cover at least one of the elements Al, Cr, Fe, Li, Mg, Mn, Nb, Ti, Sb or V and thus the elements Me1 and Me2 are respectively different, and the crystal network of the mixed crystal layer has a corundum structure, which is characterized in a spectrum of the mixed crystal layer, measured by means of X-ray diffractometry or electron diffraction, for at least three , preferably four, and particularly five lines associated with the structure of the corundum. Particularly well suited for this purpose are layer systems in which Me1 is aluminum and Me2 is at least one of the elements Cr, Fe, Li, Mg, Mn, Nb, Ti, Sb or V, and 0.2 <x <0, 98, preferably 0.3 <x <0.95. Aluminum here has a particular significance as an element for increasing oxidation resistance and thermal hardness. However, it appears that a very high aluminum content, particularly in the preparation of the layers, is problematic, since such layers, particularly at low coating temperatures, form crystallites that are increasingly smaller with the respective loss of intensity of the reflections in the X-ray diffractogram. .

[0026] To enable the growth of the layer as possibly free from disturbances and tensions, the content of halogens and noble gases in the mixed crystal layer should, in all cases, be less than 2%. This can also be achieved by the fact that fonPetição 870180015576, of 27/02/2018, p. 15/54

10/36 be driven by a process gas that consists of at least 80%, preferably 90%, particularly at 100% oxygen. Thus, the noble gas content in the mixed crystal layer can also be limited to a maximum of 0.1%, preferably to a maximum of 0.05%, and / or the halogen content to a maximum of 0.5%, preferably at most 0.1%, or in the most favorable case, the mixed crystal layer is preferably prepared essentially free of noble gas and halogen.

[0027] Regarding the construction of the mixed crystal layer, several variants are possible. For example, the layer can be introduced as a single layer or multiple layers of at least two alternately precipitated polyoxides. Alternatively, a polyoxide may be precipitated in an alternating sequence with another oxide. The polyoxides that were prepared by arc spraying or sputtern spraying of chromium-aluminum and vanadium-aluminum alloys were thus particularly resistant to high temperatures. Like other oxides for alternating coating with HfO ₂ polyoxides, Ta ₂ O ₅ , TiO ₂ , ZrO ₂ , γ-ΑΙ ₂ Ο ₃ and, particularly, oxides in the corundum structure, such as Cr ₂ O ₃ , V ₂ O ₃ , Fe ₂ O ₃ , FeTiO ₃ , Ti ₂ O ₃ , MgTiO ₂ and of course particularly a-AI ₂ O ₃ , have good properties at high temperatures.

[0028] In the preparation of the layer system, it has been shown to be advantageous to keep the layer stresses of the mixed crystal layer low, in order to allow the precipitation of thicker layers, as they are necessary, for example, particularly for fast rotating processing of metallic materials. If, in addition to the layer system, internal stress properties, defined for the processing of hardened steels, are also applied, for example, particularly sliding properties are provided for better stress flow, or for use in elements

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11/36 sliding, and better adherence to different or similar substrates, these can, for example, objectify through the appropriate choice between the substrate and the mixed crystal layer, for example, intermediate layers consisting of at least one adhesive layer and / or rigid layer, or by introducing one or more layers of cover in the mixed crystal layer.

[0029] The rigid layer or cover layer therefore preferably contains at least one of the metals from subgroups IV, V and VI of the periodic system of the elements Al, Si, Fe, Co, Ni, Co, Y. La, namely compounds of the elements mentioned with N, C, O, B or mixtures thereof, in which compounds with N, or CN are preferred. The TiN, TiCN, AlTiCN, AlCrN or AlCrCN compounds are particularly suitable for the rigid layer, while AlCrN, AlCrCN, Cr ₂ O ₃ or AI ₂ O ₃ are particularly suitable for the cover layer, particularly γ-ΑΙ ₂ Ο compounds ₃ or a- AI ₂ O ₃ . Similar to the mixed crystal layer, the intermediate layer and / or the rigid layer can also contain a layer with multiple layers. In addition, the layer system can also be constructed as a multilayer layer with alternating intermediate layer and mixed crystal layer or alternating cover layer and mixed crystal layers.

[0030] For the preparation of mixed crystals in the corundum structure, arc flash processes with or without a small vertical and pulsating magnetic field, as well as a general process, such as the arc flash or spray process, are suitable. in which in the material sources, such as arc flash evaporator or spray sources (sputter), a high tension force is produced, that is, they are superimposed and the basic operation in direct current (DC). This makes it possible to operate in the poisoned state, or to form an alloy on the target, provided that Petition 870180015576, of 02/27/2018, p. 17/54

12/36 certain margin conditions just mentioned are maintained.

[0031] With reference to the arc flash process for preparing the layer system according to the invention, in particular for preparing the oxide mixed crystal layer, reference is made in addition to the following patent applications by the same claimant who, with reference to the process, form the most recent state of the art: WO 2006099758, WO 2006/099760, as well as CH 0116/06. The entire process was carried out in an RCS coating system from Balzer.

[0032] For the preparation of mixed crystals in the corundum structure it is essential, in all processes, that the target is an alloy target, since, otherwise, at precipitation temperatures below 650 ° C, as detailed below described, it is not possible to precipitate a layer of mixed crystal in the structure of the corundum. In the sense of a process that is as simply reproducible as possible, it is advantageous to choose the process parameters in such a way that in the composition of the metals in the mixed crystal layer, after normalization regarding the total metal content, the content of the respective metal parts does not differ more than 10 percent, preferably not more than 5, in particular not more than 3 percent of the content of the target metal composition. This is achieved, for example, by maintaining the parameters mentioned in the test examples, by selecting the lowest substrate voltage, for example, below 100 V, to prevent, among others, separation of the mixture by effects on the corners. They can also be adjusted and varied by specialists according to each alloy system, among others, for example, in case it is necessary to achieve a high compression stress. [0033] Arc flash processes, in which none or only a small external magnetic field, essentially perpendicular to the target surface, is applied to the target surface, are appropriate

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13/36 for the preparation of polyoxides according to the invention. If a magnetic field with a vertical component B _z is applied, then it is advantageous to adjust the component B _r radial or parallel to the surface, at least along most of the target surface, at least in the meantime through 70%, preferably 90 % less than B _z . The vertical component B _z is adjusted here between 3 x 10 ⁴ and 5 x 10 ³ (3 and 50 Gauss), being preferred however between 5 x 10 ⁴ and 2.5 x 10 ³ (5 and 25 Gauss). Such magnetic fields can be generated, for example, by a magnet system consisting of at least one axial pole loop, which has a geometry similar to the target's perimeter. The plane of the loop can be arranged here at the height of the target surface or preferably parallel to the rear. The processes described below in greater detail with pulsating sources, can be operated particularly advantageously with an arc flash process with sources that have such a weak magnetic field. [0034] According to the following pulsating source processes for the preparation of particularly thermally stable mixed crystal layers of polyoxides in corundum-type crystal structures, at least one arc source is fed at least concurrently with a direct current and also with pulsating or alternating current. Here, it is precipitated on the part with a first electrode shown as an alloy target of an arc source or a spray source, as well as with a second electrode, the source being supplied simultaneously with a direct current or direct voltage as well as well as a pulsating alternating current or a pulsating or alternating voltage. The alloy target here corresponds essentially to the composition of the mixed crystal layer. The preferred pulse frequency is here in the range of 1 kHz to 200 kHz, and the pulsed current supply can also be operated with different proportions of width

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14/36 pulse or pulse breaks.

[0035] The second electrode can thus be arranged separately from the arc source or as an anode of the arc source, the first and second electrodes being operated with a single pulsed current supply connected. If the second electrode is not operated as an arc source anode, the arc source can be operated via the pulsed current supply connected to one of the following material sources

- another vaporizing arc source that is also connected to a DC direct current supply;

- a sputter source cathode, in particular a magnetron source, which is also connected to a power supply, in particular to a DC direct power supply

- a vaporization crucible which at the same time is operated as an anode of a low voltage arc vaporizer.

[0036] The DC direct current supply occurs here with a basic current in such a way that the plasma discharge is maintained at the correct level essentially without interruption at least in the arc flash sources, preferably, however, in all sources .

[0037] Advantageously, the DC direct current supply and the pulsating current supply are decoupled by means of an electric decoupling filter, which preferably contains at least one blocking diode. Coating can take place here at temperatures below 650Ό, preferably below 550Ό.

[0038] The polyoxide layers in this case grow, despite the comparatively lower coating temperature, and eventuPetição 870180015576, of 27/02/2018, p. 20/54

15/36 in corundum-type structures, such as adhesive or intermediate layers, for example, cubic metal nitride or carbon nitride layer, which was surprising, since in the previous tests, among which layers could be prepared by simultaneous vaporization of the tool part by means of an elementary aluminum or chrome target under oxygen and amorphous, for example, layers of (ΑΙ _10χ Ογ _χ ) ₂ Ο ₃ could be prepared. This was then the case when the coating range of the overlapping sources was adjusted. Only through the use of alloy targets is it possible to precipitate at comparatively lower process temperatures polyoxides in the crystalline structure, particularly in the corundum structure. Therefore, care must be taken to ensure that sufficient oxygen is made available on the target, so that a high oxygen content of at least 80%, preferably 90% in the process gas, is adjusted, in example 1) follows, oxygen is used exclusively as process gas. The target surface is thus coated with a thinner non-conductive layer during the arc flash process. According to the inventor's point of view, the reason for reducing the growth of crystalline layers, otherwise only possible essentially at higher temperatures, in particular the growth in structure of the corundum, could be due to the formation of polyoxides on the target surface , which evaporate during the process, first form growth germs on the workpieces, and finally take part in the growth of the layer. Such a growth mechanism can have different causes. On the one hand, the temperatures generated by the discharges on the target surface are in the range of the melting point of the alloy, so that in case of sufficiently high oxygen concentration, good preconditions for the formation of polyoxide structures of the type are present corundum stable at high temperature. On the other hand, as mentioned above, no mixed crystal

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16/36 could be prepared by simultaneous vaporization of elemental aluminum and chrome targets. Similarly, it also applies to oxide layers prepared by the sprinkling technique. Thus, tests analogous to US 6,767,627 were prepared by the inventor of the present patent application, by spraying, in layers of aluminum oxide and layers of aluminum chromium oxide in a temperature range between 400 and 650 ° C. However, no layer of aluminum oxide or crystalline aluminum oxide with a corundum structure was observed. This also does not occur in the use of alloy targets, which on the one hand could mean a failure in thermal stimulation in the usual spraying process, and on the other hand, the fact that no compound was sprayed on the target surface, but only atoms. .

[0039] When also practical proof of such a formation mechanism, for example by spectral analysis, cannot be provided at this location and possibly other mechanisms are of importance, it can be seen that with this present invention they can be prepared for the first time polyoxides with proven evident corundum structure, at a coating temperature between 450 and 600 ° C.

[0040] In order to continue to increase thermal stimulation on the target surface, individual tests were also carried out with uncooled targets, for example heated and under oxygen evaporated from the material on the target surface, hence red-hot. The layers thus prepared also show a corundum-type network. Concomitantly in such processes, an increase in plasma impedance can be seen by increasing the discharge voltage, which is due to the high electron emissions from the incandescent surfaces in combination with the high vapor pressure of the target material and is further reinforced by the pulsation source current.

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17/36 [0041] Another possibility in the preparation of oxide layers according to the invention is the operation of a high-power discharge with at least one source. This, for example, can be generated by operations of supplying pulse current or pulse voltage with lateral pulse inclination at least in the range of 0.02 V / ns to 2.0 V / ns, preferably in the range of 0, 1 V / ns at 1.0 V / ns. Here currents of at least 20 A are applied, preferably equal to or more than 60A, for voltages between 60 and 800 V, preferably between 100 and 400 V, above or in addition to the voltage and current of the DC discharge current continuously operated at the same time. These peak voltage impulses can for example be generated by one or more cascades of condenser, which alongside other different advantages also makes it possible to facilitate the supply of basic current. Preferably, the pulse generator is meanwhile activated simultaneously with two arc sources operated with direct current. Surprisingly, by applying peak impulses in the arc flash process, it is possible to raise the voltage at the source by several feet depending on the height of the applied voltage signal, while pulses with a lower lateral slope, as expected, only cause the current of the source.

[0042] As the first tests showed that it is also possible to prepare oxide oxides in corundum from spray sources with alloy targets, Eskolait or comparable hexagonal crystal structures, which is supposedly caused by the higher power density on the the target surface and the consequent high temperature rise, here too it could be advantageous to use uncooled or heated targets as described above. The discharge of high power in such processes shows, both for high power arcs as well as for

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18/36 high power, similar characteristics, as they correspond to the abnormal brightness discharge (Glimm) known from the Towsend current-voltage diagram. The approach in this context occurs here respectively from opposite sides, therefore, on the one hand of the arc discharge from the arc flash process (low voltage, high current), on the other hand from the Glimm discharge from the spraying process (medium voltage, low current) .

[0043] Basically, measures are required to increase the plasma impedance respectively or the target surface (see above), if it approaches the abnormal Glimm discharge range on the high current side, therefore on the arc side. This can, as above, be caused by overlapping peak pulses, by heating the target surface or by a combination of measurements.

[0044] Another way to increase the plasma impedance is through the pulsation of a source magnetic field. This can occur, for example by the pulsating current of the source, which either as a whole or only as a partial current is conducted through the magnet system consisting of a loop with axial polarity as described above. Corresponding to the high current peaks that occur, chilled turns with a low number of bearings (1 to 5) can be used here.

[0045] From the tests exposed above and from those described below it can be recognized that the layer systems, according to the invention in general, present an excellent suitability for tooling jobs. They can thus advantageously be used on tools such as cutters, drills, toothed tools, rotary cutting plates, chisels, cleaning needles of different materials, such as cold and hot operating steels, HSS steel as well as sintering materials such as metallurgical steel in powder (PM), carbide (HM), cermets, cubic boron nitride (CBN), carPetition 870180015576, from 02/27/2018, p. 24/54

19/36 silicon nitride (SiC) or silicon nitride (SiN). Particularly good, however, is the suitability of using tools with high operating temperatures or cutting speeds, such as lathe operations, high-speed cutters and the like, which alongside the abrasive load also place high demands on thermochemical stability of the hard layer. Nowadays, CVD-coated rotary cutting plates are used for such tools. Here, layer thicknesses ranging from 10 to 40 pm are often used. Based on the properties described above, the coated rotary cutting boards are therefore a preferred use of layers, according to the invention. Particularly rotary cutting plates of PM steel, sintering materials of carbide, cermet, CBN, SiC, SiN or rotary cutting plates previously coated with polycrystalline diamond.

[0046] Although, during the work of the present invention, in particular, the development of protective layers for cutting tools took precedence, the layers can evidently be used advantageously in other areas. For example, a good suitability can be assumed for tools for different hot deformation processes, such as calendering and forging or casting metals or alloys. Due to the high chemical resistance, the layers can also be used in tools for the processing of plastics, for example tools for injection or pressing for molded articles.

[0047] Other possible uses arise in the scope of the coating of parts and components, such as, for example, the use in parts subjected to the temperature of internal combustion engines, such as injection nozzles, segment ring, valve seat, turbine blades and similarly ordered components. They can also be used here, similarly to the above, by

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20/36 less in the areas subject to wear, the following basic materials: cold operating steel, HSS, PM steel, HM, cermet, or CBN sintering materials.

[0048] Also for layers of temperature-stable sensors, layers can be deposited according to the process according to the invention, for example for piezoelectric and ferroelectric materials to superconducting quaternary oxide layers. It is self-evident that these layers are not linked to a substrate structure and that, in such a context, they mainly offer an application in connection with MEMS on silicon base.

Examples and Figures [0049] The invention is further explained by means of examples, in which reference is made to the figures indicated by way of example, which show the following:

[0050] Figure 1 X-ray spectra of (AI _{1. x} Cr _x ) ₂ O3 layers; [0051] Figure 2 Parameter of network of layers of (AI _{1. x} Cr _x ) ₂ O ₃ ; [0052] Figure 3 Behavior of the network parameter with temperature [0053] Figure 4 Oxidation behavior of the TiAIN layer; [0054] Figure 5 Oxidation behavior of the TiCN layer; [0055] Figure 6 Oxidation behavior of the TiCN / ÍAIv ^ r ^ Oa layer;

[0056] Figure 7 Detail of the (AI _{1. x} Cr _x ) ₂ O ₃ layer _; [0057] In test 1) described below, a complete course of the coating process according to the invention is indicated with a weak magnetic field essentially vertical in the range of the target surface.

[0058] After placing the parts on the supports rotated two or three times and placing the supports in the vacuum treatment installation, the treatment chamber is emptied at a pressure

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21/36 of about 0.1 Pa (10 ⁴ mbar).

[0059] To adjust the process temperature, a low voltage arc plasma (NVB) supported by radiant heating between a cathode chamber, separated by a slit, with hot cathodes, and cathodically driven work tools are incandescent in a argon - hydrogen atmosphere.

[0060] The following heating parameters were thus adjusted:

Discharge flow NVB Argon flow Hydrogen flow Process pressure Substrate temperature Process time

250 A cm ³ CNTP 300 cm ³ CNTP 1.4 Pa (1.4 x 10 ² mbar) ca. 550 ° C 45 min [0061] Alternatives are known to the expert. The substrates were thus preferably activated as anodes for the low voltage arc and preferably additionally pulsed unipolar or bipolar.

[0062] As the next process step, corrosion / deposition begins. For this, the low voltage arc is operated between the filament and the auxiliary anode. Here too, a direct current (DC) supply, a pulsating direct current or an MF or RF supply operated with alternating current between tools and masses can be activated. Preferably, the tools are subjected, however, with a negative bias tension.

[0063] Here the following corrosion / deposition parameters were set

Argon flow Process pressure Discharge current NVB cm ³ CNTP

0.24 Pa (2.4x10 ' ³ mbar)

150 A

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Substrate temperature Process time Stress

500Ό 45 min

200 - 250 V [0064] In the next process step, the substrate is coated with an AlCrO layer and an intermediate TiAIN layer. All coating processes can, in case of higher ionization need, be supported by the low voltage arc plasma.

[0065] Here the following parameters were set for the deposition of the intermediate layer of TiAIN cm ³ CNTP (without addition of argon) pressure set at 3 Pa 3 Pa (3 x 10 ² mbar)

Argon flow Nitrogen flow Process pressure

Source direct current TiAI 200 A Source current of the magnetic field (MAG6)

Continuous stress on the substrate Substrate temperature Process time Stress

1A

U = -40 V Ca. 550 ° C 120 min. 200 - 250 V [0066] For the 15-minute transition to the self-function layer, the arc sources AlCr are connected with a DC current of 200 A, with the positive pole of the DC source being connected to the source and ground anode ring. A substrate voltage of 40 V is applied to the substrates during this step. Five minutes after the activation of the AlCr target (50/50), the addition of oxygen begins, and it occurs in a gradient of 50 to 1000 cm ³ CNTP in a period of 10 minutes. At the same time, Ti Al 50/50 targets are turned off and N ₂ is controlled at about 100 cm ³ CNTP. Just before the admission of

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23/36 oxygen the voltage on the substrate is changed from continuous to bipolar pulses, and is raised to U = - 60 V. This prepares the intermediate layer and the transition to the function layer. The targets are targets prepared by powder metallurgy. Alternatively, casting metallurgy targets can also be used. In order to reduce the frequency of spatter, single-phase targets, such as those described in De 19522331, can be used.

[0067] The coating of the substrates with the proper function layer occurs in pure oxygen. Bearing in mind that the aluminum oxide is in the insulating layer, either a pulsating voltage supply or an alternating voltage supply (AC) is employed.

[0068] The essential function layer parameters have been adjusted as follows:

Oxygen flow 1000cm ³ CNTP

Process pressure 0.26 Pa (2.6 x 10 ³ mbar)

DC direct current AlCr 200 A

Magnetic field source current (MAG6) 0.5 A, so a weak vertical magnetic field of approximately 2 mT (20 Gs) was generated on the target surface.

Positive PS substrate tension)

Substrate temperature Process time

U = 60 V (bipolar, 36 ps negative, 4

550 ° C 60-120 min.

[0069] With the processes described above, hard layers with good adhesion could be generated. Layer equalization tests on lathe and milling tools resulted in a noticeably improved service life compared to known TiAIN layers, although the roughness was visibly above the optimized roughness values of pure TiAIN layers.

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24/36 [0070] Tests 2 to 22 indicated in Table 1 refer to single layer systems according to the invention, which consist respectively of a double layer of oxide type (AI _{1. X} Cr _x ) ₂ O ₃ prepared at coating temperatures between 450 and 600 ° C. The other parameters are identical to the parameters described above for preparing the function layer. The measurement of the stoichiometric fraction of the layer composition occurred by means of Rutherford spectrometry (Rutherford Backscaterring Spectrometry) (RBS). The largest deviation from the alloy composition of the target indicated in column 2 is shown by tests 10 to 12 with a deviation of 3.5 percentage points at an Al / Cr ratio of 70/30. The metal fractions of the layer are normalized by the total metal content of the oxide. In contrast, with reference to oxygen stoichiometry, there is a slightly greater deviation, above 8%. Despite this, all the layers show a visible network structure of the corundum type. Preferably, all layers, according to the invention, should therefore present a sub-stoichiometry in relation to 0 to 10% oxygen, since a desired network structure is still formed within a range of about 15% oxygen deficit. .

[0071] Figure 1A to C shows typical corundum structures of (Ah. _X Cr _x ) ₂ O ₃ layers according to the invention which, with targets of different alloys according to test 18 (Al / Cr = 25 / 75), 14 (50/50) and 3 (70/30) were prepared at 550 ° C. Measurements and evaluations took place by means of X-ray diaphractometry with parameter adjustments detailed described in the measurement methods above. The presentation did not require a correction of the signs. The determination of the network parameters can also occur by other methods, for example by electron diffraction spectrometry. Due to the reduction in the layer thickness of Figure 1A to 1C from 3.1 to 1.5 pm, the unmarked substrate lines compared to those with layer lines

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25/36 of the corundum structure marked with dashes grow strongly. Despite this, they can also be arranged in the C spectrum, despite a linear presentation of the axes of the ordinates, 7 visible lines in the corundum structure. The remaining lines must be associated with the basic carbide material (WC / Co alloy). However, for an unambiguous arrangement of the crystal network and determination of the network constants, at least 3, preferably 4 to 5 lines, should be visibly identifiable.

[0072] The crystal structure of the layers is finely crystalline and roughly measured with an average crystalline size less than 0.2 pm, namely at a high chromium content and coating temperatures of 650 ° at crystallite sizes between 0.1 to 0.2 pm.

[0073] In Figure 2 for tests 2-22 the lattice constants a (dashed line) and c (underlined) of the crystal lattice (Ah-xCr ^ O ₃ are applied over the stoichiometric chromium content and compared respectively with three values DB1 to 3 determined by the ICDD (International Center for Diffraction Data) of the dotted line according to Vegard's law, so the total concentration range is shown over a maximum deviation of 0.7 to 0.8% from the ideal Vegard. other polyoxide layers show similar results, the deviations are at most 1% in the indicated parameters This points to very low internal stresses of the mixed crystal layer, because unlike many other layers obtained by physical vapor deposition it is possible to precipitate with a greater layer thickness, for example between 10 and 30 pm, in individual cases at 40 pm, with good adhesion Higher tensions in the layer could be obtained by placing only higher substrate tensions (> 150) and / or using a mixture of Ar / O2 from the process gas with a high fraction of Air. Since for many applications, multiple

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26/36 special layers, as described in detail below, internal stresses are well suited and can be adjusted over a wide range if necessary by choosing an intermediate layer and / or many-layer covering layer between tool and the envisaged mixed crystal layer. For example, higher internal compression stresses can therefore be adjusted to increase the hardness of the layer for hardness processing processes. For industrial applications with high abrasive wear, thick layer systems with layer thicknesses greater than 10 or 20 pm can therefore be economically prepared, with the mixed crystal layer being preferably selected greater than 5 and particularly greater than 8 pm.

[0074] At the same time, checks were made on the thickness of 2 pm of the mixed crystal layers according to the processes described above (flexure strips methods according to Stoney and flexion discs methods). Thus, the layer tension was measured in a range between tension-free and with small compression stresses or tension stresses with values less than or equal to 0.5 GPa. For precipitation of thicker layers obtained by physical vapor deposition, however , slightly higher layer stresses, of about 0.8 GPa, are also appropriate. Another possibility is a thin layer (<1 pm) precipitated by an alternating sequence of stretch stress and compression stress as layer systems multiple.

[0075] To check the resistance to temperature and oxidation of the corundum structure of the layers of (AI _{1. X} Cr _x ) ₂ O ₃ were heated, according to table 2, test 2, coated carbide test bodies , with high Co content, in a time span of 50 minutes, at a temperature of 1000 ° or 1100 ° C and kept there for 30 minutes, and then they were cooled in a time of 50 miPetition 870180015576, 27 / 02/2018, p. 32/54

27/36 minutes at 300 ° C. After cooling to room temperature, the network constants were again determined. According to the phase diagram indicated in the American Ceramic Society's Phase Equilibria Diagrams Volume XII Oxides [W. Sitte, Mater. Know. Monogr., 28A, React. Solids 451-456, 1985] in the range between about 5 to 70% aluminum, that is, (^ 0.05-0.70 ^ 0.95.0,30) 203 for temperatures around 1150 ° C, a mixing failure, which allows the mixture to be separated from the mixed crystal (AI ₁₀ xCr _x ) ₂ O3 into AI ₂ O ₃ or Cr ₂ O ₃ and a mixed crystal (AI _{1. x} Cr _x ) ₂ O ₃ from another composition. Through the diagram it is also recognizable that through the process according to the invention it is possible to move the temperature of thermodynamic formation to layers of mixed crystal (AI _{1. x} Cr _x ) ₂ from 1200 ° C to 450 ° to 600 ° C. Surprisingly, it was also shown that the mixed crystal layers prepared according to the invention through the incandescent process show only minor changes in the network constants and there is also no separation of the mixture in the binary components. The maximum deviation visible in Figure 3 of the network parameter a, measured at room temperature, according to the coating process and the calcined sample is about 0.064%, the maximum deviation of the c value is 0.34% . Also for several other polyoxides in measurements, there is an extraordinary temperature stability of the layer and a small deviation from the network constant, from a maximum of 1 to 2%.

[0076] Figure 4 and Figure 5 show the results of the oxidation tests of known layer systems by means of a REM fracture pattern of a TiAIN layer or a TiCN layer which, as described above, is heated to 900 ° C and then it was calcined for 30 minutes at that temperature under oxygen. In the TiAIN layer, a visible change in the surface structure can be recognized in a range above 200 nm. An outer layer consisting of sPetition 870180015576, of 02/27/2018, p. 33/54

28/36 essentially of aluminum oxide with layer thicknesses between 130 and 140 nm follows a layer poor in porous aluminum with layer thickness between 154 and 182 nm. Even worse is the oxidation behavior of the TiCN layer in Figure 5, which is oxidized by such a treatment to the base material and shows an initial detachment of the layer on the right side of the figure. The layer has coarse grains and no longer has the column structure of the original TiCN layer.

[0077] Figure 6 and Figure 7 show the results of an identical oxidation test on a layer of TiCN, which is protected by a layer of (Alo, ₇ Cr _o , ₃ ) ₂ O ₃ of about 1 pm according to the invention. Figure 6 shows the layer alloy at a magnification of 50,000 times. The known columnar structure of the TiCN layer and the slightly more crystalline (Al _o , ₇ Cr ₀ , ₃ ) ₂ O ₃ layer are visibly recognizable. The size of the crystallite of the aluminum chromium oxide layer thus can still be refined for example with the use of targets with a higher Al content. Figure 7 shows the alloy of the layer at a magnification of 150 000 times, the layer of TiCN can also be recognized at the bottom of the figure. Above the layers in Figure 4 and Figure 5 is the reaction zone of the (AI ₀ , ₅ Cr ₀ , 5) 203 layer with an H2 thickness of at most 32nm essentially smaller and has a layer structure without recognizable pores. In a series of comparative tests with different mixed crystal layers according to the invention it is shown that these, unlike other oxide layers of the prior art, protect the intermediate layers between them and thus provide the entire layer system with a excellent thermal and oxidative resistance. Basically, for this purpose, mixed crystal layers according to the invention can be used which, in the oxidation test described above, do not form any reaction zone that exceeds 100

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29/36 nm. Preferably, mixed crystal layers with reaction zones between 0 to 50 nm are preferred.

[0078] The hardness of the measured layers of the (AI ₀ , ₅ 010,5) 2 () 3 layers is around 2000 HV ₅₀ . Values between 1200 and 2500 HV can also be determined by measurements on other polyoxides, such as (Alo, ₅ Ti _o , 30 ^, 2) 2 () 3, or (ΑΙ _ο , ₆ Τϊο, ₄ ) ₂ O ₃ , (Vo, 5 (^ 0.5) 2 () 3, (Hello, 2 (^ 0.8) 2 () 3 [0079] In Tables 3 to 6 other multi-layer executions of the layer system are indicated, according to the invention Process parameters for preparing mixed crystal layers for AlCrO or AlCrON in a 4 source coating system (RCS) are found in Table 7, corresponding process parameters for preparing individual layers for several layers of support are found in Table 8.

[0080] Tests 23 to 60 in Table 3 and 4 thus refer to layer systems in which the oxide mixed crystal layer in the corundum structure is constructed in most individual layers. Only in test 25, 29 and 31 the mixed crystal layer is formed by two successive individual layers of different chemical composition. In test 29 the mixed crystal layers differ only by a different Al / Cr ratio.

[0081] Tests 61 to 107 in Tables 5 and 7 thus refer to layer systems in which the mixed crystal layer of 5 to 100 individual layers is formed by very thin layers between 50 nm and 1 pm. Thus, both oxide mixed crystal layers can occur in the corundum structure with different chemical compositions, as well as corresponding mixed crystal layers with other layer systems.

[0082] Comparative tests with different lathe and cutter tests produced for test layers 23, 24 and 61 to 82 in turning

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30/36 as well as in the cutter, visible improvements to known layer systems, such as TiAIN, TiN / TiAIN and AlCrN. Also compared to CVD layers on the cutter as well as for some turning applications, improved tool life can be achieved.

[0083] As indicated above, a whole series of different layer systems have already been verified and tested, and if necessary the specialist can take some known measures, if he wants to adjust certain properties of the layer system, according to the invention a special requirements. For example, the construction of other elements in individual systems or also in all layers of the system, especially in the mixed crystal layer, is taken into account. Known elements that, for example, favorably influence, at least in nitride layers, resistance to high temperatures are Zr, Y, La or Ce.

Table 1

Test No. Target [Al / Cr] Precipitation temp rci Temp. calcination [Ό] Content stoichiometric Cr / (Cr + AI) Network constants d smoke] Cr Al 0 The Ç here □ B1- Al ₂ O ₃ 0.00 2.00 3.00 0.00 4,75870 12.99290 27303 DB2 - 90/10 0.20 1.60 3.00 0.10 4.78550 13.05900 2.7269 2 70/30 550 * - 0.59 1.41 3 0.30 4.65234 13.26296 27333 3 70/30 550 - 060 1.40 2.60 0.30 4,65610 13,24537 2.7277 1.5 4 70/30 600 ' - 0.61 1.39 3.00 0.31 4.64603 13.23092 2 7303 3.3 5 70/30 550 ’ - 0.62 1.38 2 75 0.31 4,65610 13,24537 2.7277 3.0 6 70/30 550 - 0.64 1.36 3.1 0 32 4 65610 13,24537 27277 3.1 7 70/30 550 ’ - 0.63 1.37 2.90 0.32 4,65612 13.23039 2,7246 2.9 3 70/30 550 ’ - 0.67 1.33 2.8 0.34 4 68443 13.15461 2,66932 2.7 9 70/30 550 ’ - 0.68 1.32 295 0.34 4.66815 13.15461 2.7022 10 70/30 550 ° - 0.67 1.33 3 0-34 4.65810 13,24537 27277 1.9 11 70/30 550 ’ - 0.67 1.33 295 0.34 4.64804 13.23193 27292 2.5 12 70/30 550 ' - 0.67 1.33 2.65 0.34 4.63993 13.24192 2.7360 2.5 13 50/50 500 ’ - 1.01 0.99 2 60 0.51 4.69218 13,32858 27245 4.1 14 50/50 550 - 1.04 0.96 2.95 0.52 4 68403 13.31746 2 7267 1.9 15 50/50 600 ’ - 1.06 0.94 2.95 0 53 4.67996 13.33965 2 7336 3.5 16 25/75 600 ’ - 1 52 0.46 265 0.76 4,92028 13,44938 2.7336 17 25/75 500 * - 1.54 0 46 2 8 0.77 4,92464 13.43531 27283 45 13 25/75 550 ’ - 1.53 0.47 2.8 0.77 4,92053 13-44355 2.7327 3.1 19 0/100 550 ’ - 2.00 0.00 2.60 1.00 4.95676 13.58237 2 7392 21 0/100 450 ’ - 2.00 0.00 265 1.00 4.97116 13.53230 2,7323 2.0 22 0/100 500 ’ - 2.00 0.00 2.75 1.00 4.97116 13,59412 2 7346 1.7 DB3 - Cr ₂ O ₃ 2.00 0.00 300 1.00 4.95876 13,59420 2 7415

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Table 2

Test No. Target [Al / Cr] Precipitation temp [Ό] Temp. calcination [Ό] Network constants The ç here 2 70/30 550 ’ RT - - - - 4,85030 13 24484 2.7307 2 70/30 550 ° 1000 ° - - 4.85339 13.22837 2.7256 2 70/30 550 ° 1100 ° - - 4 84727 13.20028 2 7232

Test Body: carbide.

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Table 3

<fi Q AND The io d 0.3 X cT a> 2 Τ ’ a> s O Z § 2 N z H | Covering layer j V D AND 2, q to d O CSI O CO O r- q ▼ - O 04 q r- O CM q T " X CM a> 5 Τ- Ο 2 O $ § CM 2 N 2 O < 2 O < 2 k_ O < z £ < z > < Z u. ü 2 O 2 u. O 2 O < | Monolayer of mixed crystal layer | [Other oxide layers | T3 ¹ T3 O K 4 · CO O CM Ό N k. q < O CM X CM Φ 2 Τ- Ο) 2 O 5 B to O CM CO u. ' O r- < <0 O CM λ. q «Í 1 Corundo structure 1 AND Ό q co q cô O CM O to q CD O d O cô O CN O O tO q M- q O IO O 00 O poop O to O d O d v " q cô O O v O d q ’Ν’ X CM <P 2 T " 0) 2 co O CM u. O tf) <’ <O O CM 'tfS $ < co O CM tf) O in co O CM 's u ' O m cp < <0 O CM 's u * O tf) <0 < co O <M T) U. ' O < co O CM O 5— ' O B; co O <M co υ r- » <' <0 O CM ** · »» CO there ll í *. CO O CM 0Í u. <p < <0 O CM there LL φ CO O OJ δ 0) ' U- <£ <0 O 'φ Φ q < (0 O CM ** tf $ there LL ifí CO O CM there LL tn < X »» * · CO O <M ^ <n > φ < CO O CM m > tf) < CO O CM > tf) <0 O q O to O O CO O «£ * O <0 O CM O CO O CM '’Ί» O <N < | Middle layer j I hard layer j And ¹ jn Ό q CO q CO O O d O poop q cô q O CM O poop O 00 q CO q q O CD X çr Φ 2 φ 2 Z The t— 2 3 H 2 < H 2 O H 2 O H 2 The H O i— 2 § 1- 2 O i- 2 O i— 2 <£ H O 5 O * O 5 2 O > O u. O z 2 O B B B I Adhesive layer | * £ Z3 Ό CM O CO d O q 00 to d CO O V d CO d O O tn d tO O to d to d CO d X CM Φ 2 ω 2 z O 5 2 H 2 H 2 H Z H 2 H 2 l · - z H 2 H O s O $ O 5 2 H 2 > 2 > 2 L_ O z Ι- Ο 2 O 2 V. O z O < Test No. CO CN CN to CN CO CM CM OO CM cn CM O CO CO CN CO CO CO CO tn CO <0 CO CO ¢ 0 CO σ> CO O 5 3 CO V * 3 to TJ-

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Table 4

AND 3 T5 2.0 X Hey <0 2 k-. V O CM Φ CO 2 The 03 AND O O O tn P D T x? v · t— Hey O Φ T5 Π O <*> O O Φ X Ό 03 Ό CN Φ 2 Hi ** and $ z 2 2 z 03 O H P P P AND V (D rx 03 ω 2 < O α O Ο Q AND ω • 8 Σ3 AND Φ Ό Ό 03 ω $. X φ Hey' O m Φ φ 8 2 U φ T— 03 £ <u Ό 2 03 P 03 ο O 03 Ό U ç □ ε 5. O CÓ P poop P poop O O O O sf O poop P O poop O Hey O <d O ιό O Hey P O Hey 03 ura de coi Ό Ό 03 AND 03 O O X Cs? Φ 5 O O 04 « 0 » r> O Hi un <71 U. ' C0 O 04 W> Cfi U- ' O 04 P <*> O 04 Q <*> O 04 Cí σ> O Hi P. to O 04 x — x P. d O) P C0 O H C0 O 04 P_ C0 O OJ P C0 O Hi P CJ O P O O 04 P ç. 4 · ^ υ O O i— P d> cô cn cn C33 Φ Φ Φ Φ O Φ ass P < m O <r tn P < m ΙΛ fx 2 2 2 2 2 u. LL IX. u. w LU 2 < < < < <’ <’ <’ < < u— x-x R »< AND O O O O G O Ό O O O O O O ro lb_ iÒ CO ΙΩ P <D CO poop ed uS v ~ ed P □ Ό τ: ro X ç? φ 2 2 ro *ç O: AND 2 O 2 u. z O 2 2 2 2 2 P O P O 2 2 2 • ro X3 Φ AND ro O 2 φ 2 Ι- Ο < O u. O < The l · - < P O P < P 05 2 < O) 2 < 05 2 < O P < P O P ω · *** ' ç ...... ro AND π 00 to tn CO c0 GRANDFATHER O CO Hey O O O u ro O O' O' O O O ιό O O V ’ 03 £ > ω T3 ro Φ PM · ' O Ό ro X | Layer CM Φ 2 φ 2 v, O 2 k_ O Z V. O < 2 P O 5 s P § 2 P P z P 2 O < 2 P 2 P 2 P 2 O φ (O r-. oo 03 O CM CO s CO and- oo 03 O O </ 3 Φ Tf M- Tf GRANDFATHER lO to m tn tn in to X ^H J

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Table 5

O « O AND 3. Ό -1 0.5 | ro B X d φ 2 x— Φ 2 z k. N z k | Cover layer ω Q TJ tO B d O O to O O CN O d d to B d d O V " tn d O X " CN B d d d d O to B g CN O 5 T " Φ 2 z O < z O < z k. N z frog k z Ω z z k. O < z > < z kv » O < Z k. O < z N Z frog k z -Q Z z k. O < Z k. N < z k z N z k. O < Q) Ό ω 03 Ό 8 _l O d tn O d V O B O T " O B O O O O O CO O O T " O O tn O O O d d O d tn O d tn O d τ— O d O T " O d O T " O d T " O d d O d τ- O d tn O d d O d d O d O τ- O B Mixed crystal layer as multiple layers | Other ML layers * £ □ Wm TJ O O O O O tO B O tn O O O to O B O O <0 O O O x— O O O to O O O τ- Ο O to O O O tn O d O O X ” O O O r ~ O O O to O O to O O O to O B O O ro B O O x— O O O to B O O x— B O tO O B O to O B O to O B O O ro B O O CN O O O X ” d O O d X d Φ 2 X " Φ 2 z O < z u. O < z k- O < z k » O < CM O k. N tf) O £ tf) O Cf .Q 2 co O > co O CM x * "W CM k. ' υ » O* Cf > < z < k O O X ” B z k_ O < z k. O < z k. υ < Cf 0 V. N tf) £ m O .Ω z <0 O CM > <0 O CM kk q co O Cl k. N < W- * z k. O < * co O Cf Ό N k. q <’ co O Cf q 5 z > <0 O Cl k. O, <[ Corundum structure Ίξ 3 Ό O O Τ- Ο O O tO O O O X ~ ' O O tO O O O O X ~ O O O d d O O d O O O d O Ο Ο d O O O d d O O d O O r- O O O to O g T " B O to O B O O Τ- Ο O O CN O O O Csl B O O d d O O CN B O O d d o o X ^- d O O ro B O O d d O O CN O O O CN O X d <u 2 x— Φ 2 WM CO ο Cf tf) Λ k. ' υ v> (0 < co O Cf tf) Λ k- O m co < co s tf) <0 k. O tf) < co 9, tf) co k. O tf) <0 < co O Cf tf) co k. υ tf) < CO O CM tf) CO k. ’ O tf) <0 < co O Cf tf) <0 k_ ' υ 8 < CO O Cf Ί k. O tf) C0 < co O CM tf) <0 k. O s <í CO O Cf tf) co k. * υ 3 < CO O Cf tf) k. ' O tf) to O CM ** tf) k- ' υ tf) co O CM * 7?) k. ' O tf) co O Cl 'tf) k- ' O tf) co O CM tf) k. ' O tf) co O Cl tf) k_ ‘ O σ> < co O Cf tf) k. ' ü tf) < co O Cl <0 k. ' O «« CO O CM ‘’ Το k- ' O co O Cf <0 k »‘ υ CO 0 CM Φ k_ ' O <. <0 O CM <0 k. O > <r co O CM (0 k- O • tf CO O CM k. O k. CO O Cl Xf > <0 co O CM xr > C0 «Í I Middle layer O: ç π •ç O: AND rc Ç £ Í 3 Ό ο cO O cn O ¢ 0 O O ro O ro O <0 O Tf O ro O d O CN O co O ro O d O co O O ro O d O ro ο <N O co O O ro O d O Tf X d Φ 2 Φ 2 ζ < k z < k z < H z The H z <, k z < k z < k z < k z < k Z The z < k z O k z O k Z O k z Q k z O k z υ k z O k z O k ζ Q z O k υ k z < k z < k O 5 z O > | Adhesive layer and Ξ. X) CN O ro B fO O ro O ro O RO O RO B cO O <0 O cO B CN O co B co B cO B CO B <O B cO O CO B co O CO O to B Tf O CO B Tf B X ç? o> 2 T ~ 0) 2 z k O $ z k z k z k z k z k z k z k 2 l · - 2 i— z k O $ z k z k z k z k z k z k 2 i— z k z k z k z k z k z > o <r σ α kâ s d <a d <o Tf ro to <0 ro ro ro co ro σ> ro O X " Γ » CN r- CO r » Tt r- to 1 ^ ro -, s. r ^. co r- ω r- O CO co CN CO ro co Tf co to 00 CD CO

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Table 6

AND □ Ό 2.0 X CN ω 5 = z O CN 0) V) 2 Q 2 you (D AND' X3 O CN O T ~ P T " to O O T " IO O O T O O X ada of CN Φ 2 Q> z O z O z i— O < z k- O z H z i- z 1- AND ω 2 CD Q <D U O Z | layers _l O to O O V " O to O O O CN O O O T " O dog O O O LO O O O CN O O co O O V " O O CN O O V O CN O O IO O O CO O tO O O CN O O CN O O O LO 8 _l Έ * O O O O O O O O O O O O O O O O O O O O O Ό 2 ç O O O LO tf) O O O to O O O O O LO LO O O O O to CO IO O O V T— tf) O CN co T- * LO O O co LO T ~ Ç- O B CD Ό O O O O O O O O O O O O O O O O O O O O O CD XJ O $ CD AND X rt O rt O rt O rt O rt O rt O rt O rt O rt O rt O CM α · ± = - CD O CN Φ z tn rt tn rt tn rt z z CM rt CM rt CM ** rt z z CM 'rt O O z u. z z u. tn rt tn O rt z * s rt O AND ω CD t_ 3 O 2 r— Φ 2 O k_ O v> u> <' t_ O s < l_ O tn <n < 1- O O U. O í *. < U. O N. <. u. O r- <. The H "s Η- u. O f- <' O O < O < O < L_ O tn <£> < fM X5 z > L_ O tn ω < 2 8 2 O ΈΓ O O O O O O O O O O O O O O O Γ) O O O O O (/) ç O O O IO LO O O co to O to ¢ 3 O O O IO O O O O O £ 3 3 CN CN O O O Ί ~ CN O O V ^- O CN r— to O v— CN CN CN CN The cn δ L_ O Ό O O T ~ O O O O V O O O O O O O O O O O O O CD Ό X rt O fM rt O rt O rt O « O rt O rt O rt O rt O rt O rt O rt O rt 9, rt O rt q, rt O <D Ό • 3 CD l_ 3 CM Φ 2 co O d? rt O d? rt O d? rt O d? * rt O d? 'Ίη rt u. O tn t_ ’ O tn u. O m u. ' O <M ”» Η CM 'β » H ^ CM '”Σ> H σ> H. σ> CD CD H. CD H DÍ 'P H CD H φ “ CD 3 u. d> O O O O O tn ω m > n tn «N 2 2 2 2 2 LL you. u_ LL AND ω LU 2 < < <? < < < < 5 <5 «Í <T "AND. «F AND O O O O O O O O O O O O O O O CD Jil V co IO co to Ν ’ co dog CO cb ui T- CD • N Ν ’ 3 XJ CD ’T_ 'CD X3 Φ AND Layer X ç? φ 2 φ 2 2 O z O t_ O O $ O 5 O $ O $ AlCrON z k_ O < AlCrON z <> r— z < i— z O l · - z < 1- AIMgTiN z O frog 2. <* AI, Mg.Ti) 0N z ü H z < H z <J i- <D Ç CD AND to to to LO to co CO IO to CO CO LO O co O CN O O O CD > 3 O O O O O O O O' O O O O LO O Ό CD Φ Ό D AND CD X CD O CD Ό CD AND CD CN 0> 2 φ z O z t_ O z t_ O z t_ O z O z O < z t_ O z u. O z k_ O < z 1- O 5 z i- O 5 2 Η * z i- z i— z O < Z H- Z H z i- O 2 ü ¡° doj Φ K Φ r- co co 00 σ> co O CD s> CN CD co CD n · <d to CD co CD CD co <D CD CD O O Τ- Ο τ ^- CN O co O Ν ' O LO O V co O Nw O Z.h ·.

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Table 7

Material Chain from Source 1 1 I-S.2 I-S.3 I-S.4 Tension bp U 02 N2 P T [THE] [THE] [THE] [THE] M cm ^d CNPT cm ^d CNPT [Pan] [Ό] AlCrO - 200 - 200 -60 1000 - 2.6 550Ό AlCrO- AlCrN Multiple layers - 200 - 200 -60 1000 1000 2.6 550Ό System loop current font d and magnetism 0.5 to 1 A.

Table 8

Material Current Font I 1 I-S.2 I-S.3 I-S.4 Continuous voltage U [THE] [THE] [THE] [THE] M TiAIN 200 - 200 - -40 TiN 180 - 180 - -100 TiCN 190 - 190 - -100 AlCrN 200 - 200 - -100 AIMeN 140 - 140 - -80 AIMeCN 220 220 -120

Table 8

Material Air C2H2 N2 P T cm ^J cm ^J cm ^J [Pan] [Ό] TiAIN - Controlled pressure 3 550Ό TiN - Controlled pressure 0.8 550Ό TiCN 420 15-125 500-150 2.5-2.0 550Ό AlCrN - - 1000 2.6 550Ό AIMeN - - 600 0.8 500Ό AIMeCN 300 10-150 Controlled pressure 2.5 600Ό

[0084] Loop current of the magnetism source system 0.1 to 2

THE.

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Claims (46)

1. System of coating layers obtained by physical vapor deposition deposited by arc vaporization for the coating of parts, which contains at least one layer of mixed polyoxide crystal with the following composition: (Me1i-xMe2 _x ) 2O3 in which each Me1 and Me2 represents at least one of the elements Al, Cr, Fe, Li, Mg, Mn, Nb, Ti, Sb or V, and the elements Me1 and Me2 differ from each other, 1-x and x represent the stoichiometry of the Me1-Me2 alloy, said system being characterized by the fact that the crystalline network of the mixed crystal layer has a corundum structure, which is determined by at least three lines associated with the corundum structure, measured by means of X-ray diffractometry, said layer of the mixed polyoxide crystal comprising areas of at least one said element deposited in its metallic form. 2. Layer system according to claim 1, characterized by the fact that the corundum structure of the mixed crystal layer is so thermally stable, that even after 30 minutes of heating in air at a temperature of at least 1000 ° C or at least 1100 ° C, the crystal parameters a and / or c of the mixed crystal layer do not vary by more than 2%. 3. Layer system according to claim 1 or 2, characterized by the fact that the mixed crystal layer has a stoichiometric or substoichiometric oxygen content. 4. Layer system, according to claim 3, characterized by the fact that the oxygen content remains 0 to 15% below the stoichiometric composition of the compound. Petition 870180031782, of 04/19/2018, p. 6/17 2/7 Layer system according to any one of claims 1 to 4, characterized by the fact that the mixed crystal layer is thin crystalline, with a crystallite dimension of less than 0.2 pm. 6. Layer system according to any one of claims 1 to 5, characterized in that Me1 is Al, Me2 contains at least one of the elements Cr, Fe, Li, Mg, Mn, Nb, Ti, Sb or V , and 0.2 <x <0.98. 7. Layer system according to any one of claims 1 to 6, characterized by the fact that the layer of mixed crystal has a content of noble gas and halogens less than 2% respectively. 8. Layer system according to claim 7, characterized by the fact that the noble gas content in the mixed crystal layer is a maximum of 0.1% and / or the halogen content is a maximum of 0.5% . 9. Layer system, according to claim 1, characterized by the fact that the layer tension of the mixed crystal layer is so low that the deviation of the crystal parameters of the polyoxides is less than 1%, compared to the value calculated by Vergad's Law. 10. Layer system according to any one of claims 1 to 9, characterized in that the layer stress measured in a 2 pm thick mixed crystal layer is a compressive stress or a tensile stress with a value less than ± 0.8 GPa. Layer system according to any one of claims 1 to 10, characterized in that the layer of mixed crystal contains multiple layers of at least two different polyoxides deposited alternately. Petition 870180031782, of 04/19/2018, p. 7/17 3/7 Layer system according to any one of claims 1 to 11, characterized in that the mixed crystal layer contains multiple layers of at least one polyoxide and another oxide in an alternating sequence. Layer system according to any one of claims 1 to 12, characterized in that the polyoxide is a double oxide. 14. Layer system, according to claim 13, characterized by the fact that the other oxide is HfO2, Ta2Os, T1O2, ZrO2, γ-Αΐ2θ3. Layer system according to any one of claims 1 to 14, characterized in that, in addition to the mixed crystal layer, at least one intermediate layer is arranged between the tool and the mixed crystal layer, and / or the covering layer is deposited on the mixed crystal layer, and the covering layer contains one of the metals of groups IV, V, and VI of the periodic table of elements and / or Al, Si, Fe, Ni, Co, Y , La or a mixture of them. 16. Layer system according to claim 15, characterized by the fact that the metals in the covering layer are composed of N, C, O, B, or mixtures thereof. 17. Layer system according to claim 15, characterized by the fact that the intermediate layer contains a multiple layers. 18. Layer system according to claim 15, characterized in that the intermediate layer and the mixed crystal layer and / or the cover layer and the mixed crystal layer are arranged as multiple layers. 19. Layer system, according to claim 15, characterized by the fact that the layer system presents Petition 870180031782, of 04/19/2018, p. 8/17 4/7 a total layer thickness greater than 10 pm. 20. Layer system according to claim 15, characterized by the fact that the layer of mixed crystal has a layer thickness greater than 5 pm. 21. Layer system according to any one of claims 1 to 20, characterized by the fact that the crystal network of the mixed crystal layer exhibits a corundum structure which, when analyzed by X-ray diffractometry, is defined by four of the lines associated with the structure of the corundum. 22. Layer system according to claim 1, characterized by the fact that the crystalline network of the mixed crystal layer exhibits a corundum structure that, in a spectrum analyzed by X-ray diffraction, is defined by five of the lines associated with corundum structure. 23. Layer system according to claim 2, characterized by the fact that the network parameter (s) a and / or c of the mixed crystal layer do not change by more than a maximum of 1%. 24. Layer system according to claim 4, characterized by the fact that the oxygen content remains from 0 to 10% below the stoichiometric composition of the compound. 25. Layer system according to claim 5, characterized by the fact that the mixed crystal layer is finely crystalline with an average crystallite size of less than 0.1 pm. 26. Layer system according to claim 6, characterized by the fact that Me1 is Al and Me2, which is selected by at least one of the elements Cr, Fe, Li, Mg, Mn, Nb, Ti, Sb or V and 0.3 <x <0.95. 27. Layer system according to claim 8, characterized by the fact that the content of inert gas in the mixed crystal layer does not exceed a maximum of 0.05%. Petition 870180031782, of 04/19/2018, p. 9/17 5/7 28. Layer system according to claim 8, characterized by the fact that the halogen content does not exceed a maximum of 0.1%. 29. Layer system according to claim 8, characterized by the fact that the mixed crystal layer essentially contains no inert and / or halogen gas. 30. Layer system according to claim 9, characterized by the fact that the deviation of the polyoxide network parameters from the value determined by Vegard's Law is less than or equal to 0.8%. 31. Layer system according to claim 10, characterized by the fact that the tension measured in a layer of a mixed crystal of 2 pm thick represents a compression or tension effort with a value of less than ± 0.5 GPa. 32. Layer system according to the claim 13, characterized by the fact that the polyoxide is (AICr) 2O3 or (AIV) 2O3. 33. Layer system according to the claim 14, characterized by the fact that the additional oxide is an oxide that has a corundum structure. 34. Layer system according to claim 24, characterized by the fact that the oxide has a corundum structure that is Cr2O3, V2O3, Fe2O3, FeTiO3, MgTiO2 or 0C-AI2O3. 35. Layer system according to claim 15, characterized by the fact that at least one intermediate layer is an adhesive layer and / or a rigid layer, and the rigid layer contains one of the metals of groups IV, V, and VI of the periodic table of elements and / or Al, Si , Fe, Ni, Co, Y, La or a mixture of them. 36. Layer system according to claim 16, characterized by the fact that the metals of the rigid layer and / or the covering layer are composed with N or CN. Petition 870180031782, of 04/19/2018, p. 10/17 6/7 37. Layer system according to the claim 36, characterized by the fact that: the rigid layer contains TiN, TiCN, AlTiN, AlTiCN, AlCrN or AlCrCN, and the cover layer contains AlCrN, AlCrCN, Cr ₂ O3 or AI ₂ O3. 38. Layer system according to claim 37, characterized by the fact that the cover layer comprises γ-ΑΙ ₂ 03 or a-AI ₂ O3. 39. Layer system according to claim 15, characterized by the fact that it has a total layer thickness greater than 20 pm. 40. Layer system according to claim 15, characterized by the fact that the layer of mixed crystal has a thickness greater than 8 pm. 41. Piece for use at high temperatures and / or high chemical load, characterized by the fact that it is coated with a layer system, as defined in any one of claims 1 to 40. 42. Part according to claim 41, characterized by the fact that at least in areas exposed to wear, the base material of the part consists of tool steel, HSS steel, powder metallurgical steel (PM) or carbide (HM ), sintered cermets or cubic boron nitride (CBN) and at least one component consists of hot and cold operating steel, HSS steel, powder metallurgical steel (PM) or hard metal (HM), cermets, silicon carbide (SiC ), silicon nitride (SiN) or sintered cubic boron nitride (CBN) or polycrystalline diamond. 43. Part, according to claim 41, characterized by the fact that it is a cutting tool, in particular a plate Petition 870180031782, of 04/19/2018, p. 11/17 7/7 rotary cut of HSS, HM, Cermet, CBN, SiN, SiC or a PM steel or previously coated with diamond. 44. Part, according to claim 41, characterized by the fact that it is a deformation tool, in particular a forging tool. 45. Part, according to claim 41, characterized by the fact that it is an extrusion tool. 46. Part, according to claim 41, characterized by the fact that it is a component of an internal combustion engine, in particular, an injection nozzle, a segment ring, a valve seat, or a turbine blade. Petition 870180031782, of 04/19/2018, p. 12/17 1/6 ^ ΙΙΗΙ'ΉΙΊΠΙΠΝΙΙΙ, ψ JII | IJII | JIII | j | | | ,, | | | ₍ Q Γ ³ Ο Ο Ο Ο ο (suaBejuoo) epejpenb zjey 2-theta scale σ> LL 2/6 oo σ> ίι_ 2-theta scale Τι (suabejuoo) epejpenb zjey 3/6 Ο Ο) f .......... 2-theta scale (susBb) uoo) epejpenb ziey 4/6