Patent Grant
9822322
The invention relates to the coating of components and tools that are required to exhibit enhanced sliding properties or that are used in tribological systems in which as a rule lubricants have to be used to reduce friction.
The invention furthermore relates to the coating of components or tools for which there is a risk that smearing might occur during contact with the counter body or with the material to be processed. Examples of these components are piston rings, piston surfaces, injection nozzles, slide bearings, gasket rings in engines as well as generally sliding elements and gear elements. Further examples of such tools are forming tools such as pressing tools in the aluminum processing industry or plastic processing industry as well as machining tools such as drills, mills and cutting inserts for the machining of aluminum, steels and various metal alloys as well as generally forming and cutting tools.
Based on the confirmed good properties of its compounds in particular with oxygen and nitrogen, molybdenum proves to be a very interesting element for generating different composite materials that can be used for example as protective coating against wear and tear or as lubricating materials.
It is thus for example known that the presence of molybdenum trioxide (MoO3) can have an advantageous effect as intermediate material in tribological systems, i.e. a material provided between two bodies in friction against one another (such an intermediate material is usually provided as lubricant), because it causes a wear-reducing reduction of the tribological load (see for example DE102006036101 A1).
However, the production of molybdenum oxide layers in an economically sustainable way has thus far proven difficult, in particular, the production of molybdenum oxide as protective coatings against wear and tear by means of thin-film technology.
In DE102006036101 A1, a coating method is disclosed, indicated specifically for valve elements, which enables a durable solid lubricant on the basis of molybdenum to be implemented. For this, molybdenum particles were embedded in the weld seam in the frame of an electric arc welding process. When used as a valve element, molybdenum trioxide (MoO3) is formed through post oxidation, as surmised by the authors of DE102006036101 A1 so that the lubrication properties were further improved.
US20090256215 discloses several methods for generating thin molybdenum oxide layers (MoOx) for the production of gas sensors, in particular for fire detection devices on the basis of carbon monoxide (CO). According to the methods described, the object is first masked in a targeted fashion and coated with a Mo layer of 45 to 150 Å thickness by means of electron beam technology. Subsequently, the Molybdenum-coated object is annealed in air or controlled atmosphere during several days in order to enable the growth of MoOx. The authors have reported particular advantages during the growth of the molybdenum oxide phase desired by them (the carbon monoxide-selective phase β-MoO3-δ), when the annealing takes place in an O2 atmosphere at a pressure of 1.2-1.6 atm and at a temperature of 175-225° C. during 2-6 hours. The authors incidentally also mentioned that previously, for the same purpose, thin layers of molybdenum trioxide (MoO3) with thicknesses of 200 to 400 nm were produced by means of Sol-Gel and RF magnetron sputtering processes.
In Surface and Coatings Technology 163-164 (2003) 413-421, Cr2—O3/MoO3 layers produced by means of thermal spraying using powder mixtures of Cr2O3 and MoO3 were discussed. According to the authors of the article, these layers exhibit an improved reduction of the friction by comparison with similarly produced Cr2O3 layers but without MoO3.
In contrast to molybdenum oxide layers, the production and use of molybdenum nitride layers as protective coating against wear and tear have been better researched.
In Journal of Materials Science Letters 5 (1986) 255-256, the authors gave an account for example about the production of molybdenum nitride layers by means of plasma thermal spraying. The authors also commented incidentally that the examined production processes generated small quantities of molybdenum dioxide (MoO2) as a by-product. It must however be noted that MoO2 has a tetragonal or monoclinic structure and is accordingly very abrasive and thus not suitable for reducing friction (see e.g. Surface and Coatings Technology 163-164 (2003) 413-421).
Further known coating technologies for producing molybdenum nitride layers, and which are for example mentioned in Surface and Coating Technology 167 (2003) 77-82, are:
Various research papers relating to diffusion barrier, supra-conductor, catalytic and tribological properties of molybdenum nitride layers are also cited in the above mentioned publications. It is therefore to be inferred that molybdenum nitride can have specific physical, chemical and electrical properties depending on the achieved structure and that molybdenum nitride can be well suited in a wide range of applications.
Tests of phase compositions in Mo—N layers produced by means of spark evaporation have been described in Surface and Coating Technology 167 (2003) 77-82. In this connection, it has been observed that the phases in Mo—N layer systems produced by means of spark evaporation can be adjusted in a targeted fashion by varying the nitrogen pressure, substrate bias and substrate temperature.
DE19944977 B4 describes a method for increasing the boundary lubrication of low-alloyed steel with lubricated contacts in a fuel injection system. The method has the steps of preparing a low-alloyed steel substrate and then forming a metal nitride coating or a diamond-like carbon coating on the low-alloyed steel substrate, namely by using a physical vapor deposition resp. PVD process at low temperature. The authors also state that these coatings of fuel system components work to the effect that they improve the lubricity of certain fuels with low lubricity and thus reduce or minimize the need for adjuvant lubricants for the fuel compositions with lower lubricity. In terms of the method described above, the authors mention, among other nitrides, molybdenum nitride as a suitable nitride for the coating.
Surface and Coatings Technology 174-175 (2003) 713-719 reports that when PVD-produced molybdenum nitride layers are used in tribological applications and are thus, because of the friction subjected to oxidative conditions at high temperatures, the molybdenum nitride layers oxidize. The authors further show that when the molybdenum nitride layers oxidize, the properties of the oxidized layer surfaces start to dominate the friction and wear and tear mechanisms.
The coating with molybdenum also make it possible to have good sliding properties, as is disclosed in DE29620687 U1. This document describes a process for producing a coating for surgical instruments of steel. In order to produce the coating, the surgical Instrument is placed in a nitrogen atmosphere. In this nitrogen atmosphere, an electric light arc is generated and for this purpose electrodes of an alloy containing nitride formers are used. The electrodes evaporate in the light arc. The evaporating metal atoms are deposited onto the steel, where they combine with the nitrogen. The alloys used for the electrodes preferably contain titanium and/or chromium as well as aluminum. Titanium and/or chromium and/or if necessary molybdenum are preferably used as metallic nitride formers. For this purpose, a more or less large proportion of aluminum can preferably be added. The authors report that the coating thus produced has the following advantageous properties:
SU1832751 A1 discloses that when insufficient layer bonding of molybdenum nitride (No—N) layers to the substrate occurs, corresponding substrate pre-treatments for improving the layer bonding can be carried out.
In JP2006255708, Ishikawa comments on abrasion-resistant coatings that contain among others the following components:
The following applications and production methods of layers containing molybdenum, in particular of layers containing MoN and molybdenum oxide, are furthermore known:
It is interesting to bear in mind the post-oxidation effect shown in EP1783244. Yamamoto et al, report in this document about hard surface coatings for cutting and forming tools, comprising at least one nitride or nitride carbide layer containing molybdenum or tungsten and that are deposited by means of sputter and/or arc techniques and whose surfaces post-oxidize probably at temperatures close to the temperatures occurring close to the sliding surfaces. Yamamoto et al, mention her MoO2 and MoO3 as products of the post-oxidation of the Mo—N layers.
This post-oxidation effect however has the following disadvantages:
The present invention has the task of proposing an improved layer and a method for producing same, which in addition to other good tribological properties and/or electrical properties in particular also has good and stable lubrication properties and/or an improved smoothness and which preferably additionally also attenuates at least partially the above-mentioned disadvantages of the layers known so far.
Inventive Solution to the Task
According to the invention, the task is solved by the production of a hard material layer comprising a stabile oxide of molybdenum.
In particular, the task is solved according to the invention by the production of a nitride oxide layer of molybdenum Mo—(N—O) comprising a stable oxide of molybdenum.
Furthermore, an inventive controlled PVD process is proposed that allows oxygen to be made to react in a targeted fashion with molybdenum so that a stable molybdenum oxide combination is formed in the layer.
In particular, an inventive controlled PVD process is furthermore proposed that allows oxygen to be integrated in a targeted fashion into the MoN essentially without MoO2 and/or MoO3 compounds being formed in the layer. Optionally, it is possible by means of the inventive process for a MoO3 layer as solid lubricant to be deposited at the surface.
An inventive layer system according to a preferred embodiment comprises at least one of the following two layers with an oxygen concentration 0.03, and preferably comprises at least the two following layers:
Production of an inventive layer preferably takes place under process conditions for which during the PVD process for producing a PVD layer in a non-reactive gas atmosphere or in a reactive gas atmosphere (without adjunction of oxygen) gradually the reactive gas supplied in the chamber is partly replaced with the oxygen and thus molybdenum monoxide (MoO) is formed in the layer. The molybdenum required for producing the molybdenum monoxide (MoO) in the coating chamber is supplied from a target containing molybdenum and which is accordingly integrated in a PVD source, preferably in an arc evaporation source. The PVD source with the molybdenum-containing target must be activated at least shortly before the adjunction of oxygen in the coating chamber.
Molybdenum oxide (MoO) is advantageous compared with molybdenum dioxide (MoO2) and molybdenum trioxide (MoO3) in that:
The process preferably takes place under process conditions for which in pure nitrogen atmosphere the hexagonal phase of molybdenum nitride (MoN) is produced but wherein, through the adjunction of oxygen, the nitrogen is gradually replaced partially by the oxygen and thus molybdenum monoxide is formed in the layer. Since molybdenum oxide (MoO) even in the case of mechanically challenging applications remains stable and present on the layer, ft prevents or inhibits an extensive post-oxidation of the MoN layer and thus also stabilizes the molybdenum nitride.
The inventive synthesized layers exhibit neither the typical molybdenum dioxide peaks nor the molybdenum trioxide peaks in the x-ray spectrum. These layers however show during analysis (e.g. in quantitative elemental analysis by means of Elastic Recoil Detection (ERD) of high-energy heavy ions) an oxygen content of more than 3 at % but less than 50 at %, if correlating the oxygen to the pure MoO monoxide.
For specific applications, further elements such as carbon (C), boron (B), silicium (Si), tungsten (W) or copper (CU) can be added to the molybdenum nitride oxide layer Mo—N—O.
For many types of steel, the problem arises that they smear on the surface of component elements or tools coated with conventional coatings such as e.g. TiAlN or CrAlN, which is an undesirable effect in particular for the machining of metals, such as for example turning, broaching or milling. The inventors have furthermore determined that the smearing of such types of steel is prevented at least for the most part through the coating with MoN by means of spark evaporation.
This also applies in particular when molybdenum nitride is integrated in suitable quantities into other nitrides. This means that the originally very good properties that the basis nitrides have, are preserved, but that additionally smearing can be prevented by adding molybdenum nitride. Here too, the depletion of the MoN through uncontrolled post-oxidation can be prevented or at least inhibited by replacing to a greater extent or completely MoN partly with MoO, preferably at the layer surface.
Furthermore, the inventors could produce for the first time by means of spark evaporation and pulsed spark evaporation relatively thick molybdenum-containing layers (>50 nm) with a higher concentration (≧50 at %) of molybdenum oxide.
The synthesis of the molybdenum nitride oxide layers Mo—N—O in a PVD process takes place through plasma-assisted reactive coating, for example by means of reactive spark evaporation, in that a cathodic spark on a molybdenum target is operated in nitrogen atmosphere between typically 0.1 Pa and 10 Pa. The adjunction of oxygen results in the formation of molybdenum oxide Mo—O compounds.
The known oxides that are formed from molybdenum, namely MoO2 and MoO3, have as described the property that they are readily volatile. It is known that MoO3 sublimates at temperatures between 500° C. and 600° C., i.e. it transitions into the gaseous phase. In a reactive plasma, this transition into the gas phase takes place due to the high reactivity of the plasma at considerably lower substrate temperatures. This means that the transition is caused rather through the reactivity of the plasma than through the substrate temperature. This in turn means that the gaseous Mo—O compounds must be controlled very accurately so that the integration of the solid lubricant in the form of powdery molybdenum oxide (MoO2 or MoO3) during the layer deposition can be prevented.
For illustration purposes, this will be discussed using the example of some scanning electron microscope pictures (SEM images) of rupture cross-sections for Mo—N, Mo—O and Mo—N—O layers.
The inventors have deposited a molybdenum nitride MoN onto a bonding layer of chromium nitride CrN (thickness of the bonding layer approx. 300 nm). The MoN layer was produced at a temperature of 450° C. with a Mo target and a spark current of 220 A. The nitrogen pressure was 3.5 Pa and a substrate bias of 20V was used.
The SEM image of the rupture cross-section shows a dense layer morphology. Hardness measurements yielded typical values of HV 3000±500. The layer showed in comparison with layers usually produced by means of spark evaporation an unusually low roughness of Rz=1.07 μm and Ra=0.13 μm.
Additionally, the friction coefficients of the deposited layers were determined. For this, a SRV test resp. a tribometer from the company Optimol Instruents Prüftechnik GmbH was used. When performing the SRV test, the two test objects mounted in the testing chamber (a sphere on a disk) were pressed onto one another with a prescribed force. During the measurement, the upper test object, in this case the counter body (an uncoated sphere of 100Cr6 steel) oscillated on the lower test object (the coated test disk). For the measurement, the frequency, glide path, test force, test temperature and test duration were pre-specified. During the measurement, the friction forces were recorded continuously by means of a sensor and the friction values thus computed automatically. The wear and tear occurring during the measurement on both test objects was also assessed after the measurement.
The measured friction coefficient and the observations with respect to the smearing of the used counter body of 100Cr6 steel on the test disks coated with MoN in the SRV test are indicated in table 1. For all measurements in the SRV test, the same parameters in terms of frequency, glide path, test force, test temperature and test duration were pre-specified. However, the measurements were performed after three different test procedures, as is also indicated in table 1.
Since for all measurements a counter body resp. a sphere of 100Cr6 steel was used, the appearance of smearings from the steel on the contact surface of the coated test disk was to be expected, as is usual under the predefined conditions. However, the inventors surprisingly observed that no smearing of the counter body on the surface of the test disks coated with MoN occurred.
The x-ray diffraction (XRD) spectrum in
The SEM image of the rupture cross-section shows a clear transition to a loose layer construction in the last third of the layer (as sketched in
The upper layer showed the loose deposited MoO3 layer that has smearing properties but barely any mechanical resistance.
It will be obvious to the one skilled in the art that the integration of such a layer into a layer system will lead to bonding problems. The inventors ascribe this undesirable construction in the last third of the layer to the fast reaction of the molybdenum atoms in the coating chamber and even in the already produced MoN layer with the oxygen added in the coating chamber. This fast reaction, so the inventors surmise, promotes from a specific flow of oxygen onwards the formation of volatile molybdenum oxides such as MoO2 and MoO3 during coating.
This result therefore underlines the importance of preventing the sublimation of the MoO2 and MoO3 during coating, i.e. to control the flow of oxygen in such a manner that essentially not only volatile molybdenum oxides such as molybdenum monoxide (MoO) are integrated into the layer system.
It can however be advantageous according to the invention to work with a high oxygen flow until completion of the layer for molybdenum trioxide (MoO3) to be formed at the layer surface and thus for a soft run-in layer to be generated, e.g. MoO3 onto MoO.
For the layer sketched in
The friction coefficient of these layers as measured in this way was 0.75, which is surprisingly higher than the friction coefficient of the pure MoN layers which were characterized in exactly the same test conditions (same test parameters and same testing procedure) in the SRV test. The inventors conjecture that this unexpected result is due to the possibly integration of molybdenum dioxide (MoO2) in the Mo—N—O. As is known in the literature and has already been mentioned above, MoO2 is strongly abrasive. How the formation of MoO2 can be avoided in the inventive production process will be described further below.
The production process performed according to the invention essentially results only in a phase formation of the molybdenum monoxide (MoO) in the MoN layer, wherein the atomic concentration of the oxygen in the Moz(NdOe) layer lies between a value of e=0.03 and 1 under the condition z≧d+e, with d, e and z at %.
The proportion z−(D+y) of Mo then corresponds to the molybdenum that has not reacted with nitrogen and/or oxygen. This occurs for example during spark evaporation in the form of conglomerates integrated into the layer that arise from molybdenum that has not fully reacted and that are known in professional circles as droplets.
The layer sketched in
By means of energy-dispersive X-ray microanalysis (EDX), it has been established that the inventive layers thus deposited exhibit a proportion of more than 10 at % of oxygen.
However, no distinctive molybdenum dioxide or molybdenum trioxide peaks could be detected in the XRD spectrum of this layer (see
It is thus shown that the Mo—O layers produced with spark evaporation can be controlled over the oxygen flow in such a way that the stable and ductile MoO (molybdenum monoxide) can be produced and be integrated into a MoN matrix or also be synthesized as individual layer. The transition to MoO3 with or with very little integration of the abrasive MoO2 into the layer can be achieved in a fast oxide ramp and the production of a solid surface lubrication is thus possible in the same process.
As already mentioned above, an outer MoO3 layer produced in this way is particularly well suited as run-in layer.
Thanks to the flexibility of the inventively used spark evaporation and pulsed spark evaporation processes, the inventive MoO layers can also be integrated into any kind of layer. The MoO layers and MoO+MoO3 layers using MoO3 as run-in layer are integrated in particular as outer layers in order to be able to achieve a specific softness or an improved run-in behavior by comparison with the original layer system, in order for example to minimize the wear and tear of counter bodies in a tribological system and simultaneously have a stabilized oxidation behavior of layers containing molybdenum.
The integration of MoO in any kind of layer and in particular in other oxide layers such as Al—O, CrO, Zr—O, Ti—O and/or also in mixed oxide layers such as (Al, Cr)O, (Zr, Cr)O or Cr—O is also advantageous, e.g. to adjust smoothness.
For this, the reactivity of the other elements towards the oxygen must be observed very carefully. It is for example possible, through different tests each with incrementally increased oxygen flow, to analyze from which oxygen flow onwards molybdenum dioxide and molybdenum trioxide are formed in the layer. If during the coating process itself the lower oxygen flows are chosen, the formation of the undesirable molybdenum oxides is prevented.
As the inventors were able to determine, it is particularly advantageous to provide a layer containing MoN between the MoO layer and the substrate. This also contributes to further improving the mechanical stability of the layer in terms of hardness and bonding within the layer.
It can then be advantageous to provide, in addition to the molybdenum, further other metal components in the layer.
One particularly preferred embodiment of the invention is the production of a Mo—N—O layer by means of spark evaporation and/or pulsed spark evaporation, which can be produced for example as follows:
Similar layer systems can also be produced with alloyed targets of Mo in combination with other metals or by activating resp. evaporating, in addition to the Mo target or the Mo targets, also targets of other metals and/or alloys and/or of other materials during the coating process.
In order to produce similar layer systems as the ones already mentioned above but with particular mechanical properties, the inventors have also provided for inventive layer systems that comprise carbide. These layer systems are also produced by means of spark evaporation and/or pulsed spark evaporation by letting in additionally a gas containing carbon during the coating procedure and/or by activating resp. evaporating carbon targets and/or targets containing carbon.
In general terms, there is an inventive layer system according to a particularly preferred embodiment if at least two layers comprise:
The transition between the first and the second layer can be designed to be gradual.
An essential improvement of the toughness is achieved by depositing multi-layer coatings. Simultaneously, it is possible in this manner to prevent crack propagation from the surface to the basic material. Furthermore, the maximum layer thickness can be increased in many cases since internal mechanical stresses in the layer can be reduced with the multi-layer structure as compared with a monolayer coating.
In order to ensure a good cohesiveness within the entire coating, a corresponding adaptation of the material properties of the individual layers is required. This can be achieved for example by generating graded boundary/transition layers or by depositing intermediate layers.
The following examples serve to present the invention in detail, they are now however to be considered a limitation of its scope.
It is generally advantageous for piston rings and shaft seal rings to exhibit good mechanical stability and simultaneously good lubricating properties and/or smoothness. In the present example, a piston ring of stainless steel was coated with Mo—N by means of spark evaporation. For this, the piston ring is placed in the coating chamber of a coating facility. The coating chamber is evacuated and, in order to clean/activate the surface, the surface is heated and etched before the coating procedure. After letting in nitrogen into the coating chamber, a spark is ignited in the nitrogen atmosphere on a molybdenum target serving as cathode, which results in the evaporation of molybdenum and/or already reacted molybdenum nitride. The deposition of the material onto the piston surface results in the formation of a 2 μm thick Mo—N layer. The coating process enables the coating thickness to be adapted depending on the application.
The inventive coating of pistons with Mo—N by means of spark evaporation has led the inventors to the observation that the friction during the operation is considerably reduced and also the service life of the piston ring is considerably increased. The inventors ascribe the reduced friction among others to the spatterings or droplets but into the layer by the spark evaporation. These spatterings or droplets are numerically so few that they do not essentially impair the stability and thus the hardness of the Mo—N layer yet are present in such numbers that the molybdenum thus available further improves, thanks to its lubricating properties, the already good sliding properties of the Mo—N layer which is smooth due to the production process.
A particular advantage of spark evaporation is the possibility of coating functional surfaces of precision components since the layer thickness can be deposited exactly according to the required precision reap. the requirements in the tribological system.
If for the above mentioned coating method pulsed technology is used, the growth of different phases of Mo—N can be very well regulated by adjusting different pulse parameters when applying a pulsed bias voltage and/or when operating a pulsed spark evaporation source. This makes it possible, by a specific adjustment of the coating parameters and especially of the pulse parameters, to promote the growth of a particular phase and to produce Mo—N layers with particular properties, adapted to the use of the coated component, R is also possibly, by varying the coating parameters during the coating process, to build for example also in an alternating fashion multi-layer Mo—N layers with different phases. In particular, a layer system can thus be achieved in which cubic Mo—N alternates with hexagonal Mo—N. Such a layer system, which comprises at least two layers, then includes at least one cubic and thus hard layer and an outer hexagonal and thus softer layer.
According to a further embodiment of the present invention, a two-layer coating system can be deposited onto the function surface resp. onto the substrate 1, e.g. for particularly heavy-duty pistons in combustion engines or also in order to be able to dispense with external intermediates: the first layer is then a Mo—N layer and the second layer is a molybdenum monoxide layer 9, as represented in
Here too, as already described further above, an additional bonding layer can be provided, as shown in
The transition between the first layer 5 and the second layer 9 can be designed as a gradient in such a manner that with increasing distance from the surface of the substrate, the Mo—N concentration diminishes and simultaneously the Mo—O concentration increases. This results in a very good adhesive strength within the layer system. This applies accordingly for all layer transitions of the layer systems mentioned in this description. The gradient can in particular comprise the entire layer and/or the entire layers.
A further improvement of the toughness in the layer system can be achieved by the deposition of several nano-layer coatings or by producing nano-composite structures, for example by embedding the harder phase in the form of nano-grains in a matrix from the softer phase.
One speaks of X-layer, in the frame of the present description, when the layer contains predominantly X, wherein X can be an elementary material or a compound.
In the frame of the present description, a coating has been disclosed which comprises at least a layer containing molybdenum and which is characterized in that the molybdenum is essentially molybdenum monoxide.
The inventive coating can contain for example a molybdenum oxide layer comprising essentially molybdenum monoxide. A MoO layer can be distinguished from MoO2 and MoO3 layers in that for example the XRD spectrum of the molybdenum monoxide layer (MoO) exhibits essentially neither MoO2 peaks nor MoO3 peaks.
A preferred embodiment of the inventive coating can for example additionally also comprise a molybdenum nitride layer.
The inventive coating can also contain a Mo—N—O layer comprising molybdenum-nitrogen compounds and molybdenum-oxide compounds, wherein essentially the molybdenum atoms build a compound with maximum one oxygen atom and wherein molybdenum monoxide is preferably comprised in the coating.
A preferred embodiment of the inventive coating with at least one Mo—N—O layer is characterized in that the Mo—N—O layer lies between a molybdenum nitride layer and a molybdenum monoxide layer.
The atomic concentration ratio in the Mo—N—O layer can be described by the following formula: Moz(NdOe), wherein:
e: is the atomic oxygen concentration in the Mo—N—O layer
d: is the atomic nitrogen concentration in the Mo—N—O layer
z: is the atomic molybdenum concentration in the Mo—N—O layer and z≧y.
The Mo—N—O layer can also be a graded layer, wherein the oxygen concentration decreases from the boundary surface close to the substrate towards the boundary surface close to the surface of the Mo—N—O layer whilst the nitrogen concentration increases.
An inventive coating can also be deposited as a multi-layer coating system, wherein several MoN and MoO layers are deposited in alternating fashion and can also contain several Mo—N—O layers that lie for example between the MoN and MoO layers and that can be deposited as graded layers with adapted variations of the nitrogen and oxygen concentrations to improve the adhesive strength within the layer.
The inventive coating can also additionally include a cover layer with MoO3 if the MoO3 produces significant advantages for the specific application.
According to the invention, the coating can also include one or several bonding layer(s) and/or functional layer(s) between the base body and the layer containing Mo.
An also preferred variant embodiment of the invention is a coating that comprises at least one layer containing Mo and having in particular very high mechanical stability and containing (Mo1-x, Mex) AaBbCc, wherein 0≦x≦0.99, preferably 0≦x≦0.5 and Me is a metal from the group of W, Ti, Al, Cr, Si, Zr, Ta, Nb, Ag, Cu and V or the combination of two or more metals of this group and
A is nitrogen (N) with 0.5≦a≦1
B is carbon (C) with 0≦b≦0.5
C is oxygen (O) with 0≦c≦0.5
and wherein a, b and c indicate in at % between the elements N, C and O with a+b+c=1 and additional further elements can be provided but are preferably not provided, and x≧c.
A preferred variant embodiment of the invention is also a coating that comprises at least one layer containing Mo and having in particular very good lubricating properties and sliding characteristics and containing (Mo1-y, Mey) AuBvCw, wherein 0≦y≦0.99, preferably 0≦y≦0.5 and Me is a metal from the group of W, Ti, Al, Cr, Si, Zr, Ta, Nb, Ag, Cu and V or the combination of two or more metals of this group and
A is nitrogen (N) with 0.5≦u≦1
B is carbon (C) with 0≦v≦0.5
C is oxygen (O) with 0.5≦w≦1
and wherein u, v and w indicate in at % between the elements N, C and O with u+v+w=1 and additional further elements can be provided but are preferably not provided, and y≧w.
Preferably, a coating could also be structured according to the invention to comprise:
A preferred variant of the method for producing the inventive coating is a PVD process or combined PVD/CVD process, wherein the molybdenum monoxide is deposited in the molybdenum-containing layer by means of spark evaporation.
A further preferred variant of the method for producing the inventive coating is a PVD process, wherein the molybdenum-containing layers are produced by means of spark evaporation of at least one target containing molybdenum in a reactive atmosphere.
As material source for the layers containing molybdenum, both molybdenum targets as well as alloyed molybdenum-containing targets are used that are produced for example by metallurgical smelting or powder-metallurgically.
Components can be coated depending on the application with the most suitable variant of the inventive coating.
In particular, machining tools and forming tools that are coated according to the invention for the production of components of metal or metal alloys, in order to reduce or preferably completely prevent smearings of the machined metals or metal alloys on the coated surface of the tool.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2010 053 751 | Dec 2010 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/004990 | 10/6/2011 | WO | 00 | 7/22/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/055485 | 5/3/2012 | WO | A |
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| 20060042728 | Lemon et al. | Mar 2006 | A1 |
| 20070003693 | Lee et al. | Jan 2007 | A1 |
| 20080179430 | Campion et al. | Jul 2008 | A1 |
| 20090256215 | Novak et al. | Oct 2009 | A1 |
| 20090269600 | Ramm et al. | Oct 2009 | A1 |
| 20100078314 | Taylor et al. | Apr 2010 | A1 |
| 20100167463 | Sung | Jul 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 296 20 687 | Jan 1997 | DE |
| 199 44 977 | Apr 2000 | DE |
| 10 2006 036101 | Feb 2007 | DE |
| 1 146 140 | Oct 2001 | EP |
| 2006-255708 | Sep 2006 | JP |
| 1 832 751 | Jan 1998 | SU |
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| 2010020362 | Feb 2010 | WO |
| Entry |
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| Suszko, et al., “The Role of Surface Oxidation in Friction Processes on Molybdenum Nitride Thin Films”, Surface and Coatings Technology, Elsevier, Amsterdam, NL, vol. 194, No. 2-3, May 1, 2005, pp. 319-324. |
| Number | Date | Country | |
|---|---|---|---|
| 20130303414 A1 | Nov 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61407656 | Oct 2010 | US |
