Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/0021—Reactive sputtering or evaporation
  • C23C14/0036—Reactive sputtering
  • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
  • C23C14/025—Metallic sublayers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0605—Carbon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0635—Carbides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/14—Metallic material, boron or silicon
  • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/14—Metallic material, boron or silicon
  • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
  • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/24—Vacuum evaporation
  • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
  • C23C14/325—Electric arc evaporation
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
  • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
  • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
  • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications

Definitions

• the invention relates to a multiphase component wear protection layer according to the preamble of patent claim 1, a PVD component wear protection coating method according to the preamble of claim 8, as well as an apparatus for carrying out a component wear protection coating method according to the preamble of claim 15.
• the invention relates to a novel improved laminate which protects components against wear, a novel process for the Verschleisstikbe- coating of components, and a device which allows this laminate with the inventive method applied to component surfaces.
• a novel improved laminate which protects components against wear
• a novel process for the Verschleisstikbe- coating of components and a device which allows this laminate with the inventive method applied to component surfaces.
• the layers should have a minimum hardness of 15 Gpa, preferably 20 GPa and an adhesion of at least HF3.
• Teer et al. again suggest that the wear rate of the layer should not exceed the value of 10'16 rn 3 / Nm, that the Vickers hardness should be above 1000VHN and the critical load in the bond should exceed 70 N and that the dry friction coefficient should be below 0.1.
• Layers of this prior art state of the art consist of a matrix of hydrogen-containing carbon with embedded carbide crystals, with tungsten, titanium, chromium and others being used as the carbide formers.
• a multi-load gen slaughter by modulating the concentration of the carbide crystal at a frequency of about 4 nm.
• the method used is also the hybrid process of cathode sputtering and cathodic sputtering-activated acetylene pyrolysis, also referred to as dimpling process, the details of which are also described in DE10005612.
• a component wear protection layer is the requirement for a minimum layer thickness on all functional surfaces.
• the surface of components is not perfectly smooth, but has a roughness, resulting from the last processing step. This roughness is determined by standardized methods and characterized by the two parameters R 3 and R 2 .
• the layer thickness of a component wear protection layer should be at least 4 times the R 2 value, which corresponds to a layer thickness of at least 5 ⁇ m for most components.
• Strondl et al. instead of the carbide concentration modulation layers, multiple layers of carbide and carbon are proposed.
• these Layers with a diamond carbon bond should be the layer thicknesses of the carbide layers 1-3 nm, preferably 2 nm and the layer thicknesses of the carbon layers 1-20 nm.
• the layers preferably contain hydrogen.
• Burger et al. in US6869676 use instead of the layers with carbide concentration modulation multiple layers of hard materials and carbon, wherein the Schichparan should be in the range of 1-10 nm, preferably 2-5 nm.
• these problems can be avoided by avoiding hydrogen in contrast to the previous suggestions for improvement in the component wear protection layers, ie the layer contains no hydrogen, and suppresses the multilayer formation as far as possible.
• An investigation of the binding character of the layers can be omitted. Since the quality of this component wear protection coating according to the invention does not depend on the two parameters carbon bond type and hydrogen content, these layers can also be applied with uniform quality to all functional surfaces of a component.
• CVD chemical vapor deposition methods
• PVD physical vapor deposition methods
• a gas is introduced into the coating system which reacts with the steam introduced on the workpiece surface by physical processes.
• gases are oxygen, nitrogen, water vapor, hydrocarbons, boranes and hydrogen sulphide or simple compounds such as carbon oxides or nitrogen oxides, in order to precipitate metal oxides, oxides, nitrides, carbides, borides, sulfides or oxycarbides and oxynitrides. If a pyrolyzed product of the introduced gas, such as free carbon or free sulfur, is also incorporated into the layers, this is referred to as hybrid processes.
• non-reactive processes Processes in which only small amounts of reactive gas are introduced in order to avoid loss of stoichiometry are referred to as non-reactive processes.
• the widespread industrial process of oxide coating by oxide evaporation with the addition of small amounts of oxygen may serve as an example.
• Most of the processes for depositing metal carbon layers are ameliorative variants of the hybrid method already proposed by Hübsch and Dimigen, in which cathode sputtering of a metal or carbide is combined with plasma gaseous hydrocarbon pyrolysis, a plasma activated CVD process.
• the improvements relate either to the process design of the CVD process as exemplified by US6372303 or the replacement of cathode sputtering by cathodic arc evaporation, as proposed by J.
• Metalloids - also called nonmetals - are chemical elements that form covalent or ionic compounds with metals. These are the halides, the chalcogenides, nitrogen, phosphorus, arsenic, carbon, silicon, germanium and boron. (See Materials Science and Engineering: An Introduction, William D. Callister Jr., John Wiley & Sons Inc. 5th edition, section 2.4)
• magnetron sputtering devices and cathodic arc evaporators have been used in various combinations.
• the four physical vapor deposition devices furthermore comprise power supplies 10, 11, 12, 13, whose negative output is connected with cables 13, 14, 15, 16 to a plate of material to be introduced into the transport phase with physical processes, referred to below as the target plate.
• the target plate is also the surface of the physical vapor sources.
• the positive outputs of the power supplies 10, 11, 12, 13 were connected to earth.
• the chamber was also grounded with a ground wire 18.
• the magnetron sputtering devices and the cathodic arc evaporators were state of the art.
• FIG. 2 schematically shows a detail of the system 1.
• it contains a magnetron cathode sputtering device 3 and a cathodic arc evaporator 5. Details of these devices are known from the prior art.
• the magnetron sputtering apparatus and the cathodic arc evaporator each consist of a base body 23, 24, which contains the cooling devices and the devices for generating the magnetic fields, a target plate 24, 27 and target plate fastening devices 25, 28.
• the magnetron sputtering apparatus 3 is surrounded by an anode screen 26, while the cathodic arc evaporator is surrounded by an arc-limiting screen 29.
• FIG. 3 shows electron microscopic multilayer films according to the prior art.
• FIG. 3a is a bright light image with the usual magnification.
• FIG. 3b is a high resolution detail of FIG. 3a.
• Figure 3c shows the distribution of the element chrome for the same section as Figure 3b.
• 3d shows the distribution of the element carbon for the same section as 3b and 3c.
• FIG. 5 is an electron micrograph of a component wear protection layer according to the invention.
• FIG. 6 is a greatly enlarged photomicrograph of a section in a calotte cut of a component wear protection layer according to the invention.
• Figure 7a is a high resolution section of Figure 5.
• Figure 7b shows the distribution of the element chrome for the same section as Figure 7a.
• Fig. 7c shows the distribution of the element carbon for the same section as Figs. 7a and 7b.
• FIG. 8 is an example of an arc-root-point guide according to the invention for a round cathode. It is explained in Example 12.
• Example 1 The invention will now be explained in more detail by way of examples.
• the examples represent preferred embodiments.
• Example 1 The invention will now be explained in more detail by way of examples.
• the examples represent preferred embodiments.
• Example 1 Example 1 :
• FIG. 1 A system as shown in FIG. 1 was used.
• the system was equipped with 4 magnetron sputtering devices 3, 4, 5 and 6, which were equipped with target plates 24 made of chrome.
• As power supplies 4 current controlled high voltage supplies 10, 11, 12, 13 were selected.
• Finely ground martensitic stainless steel discs and hardened steel piston ring portions and bushings 20 of aluminum alloy common to these components were used as workpieces 19. These were cleaned by a prior art industrial cleaning method and mounted on the workpiece and component carriers 9.
• the chamber was pumped to a pressure of 4 mPa.
• the component carriers were set in a rotational movement 21 at a speed of 3 revolutions / minute and the component carriers of the cylindrically symmetrical components were additionally set in an autorotation 22.
• an argon pressure of 0.3 Pa was set in the chamber.
• the high voltage supplies 10, 11, 12, and 13 were turned on and a current of 7 amps each was set.
• the argon gas was replaced with a 1: 4 mixture of argon: acetylene and the pressure was simultaneously raised to 1 Pa.
• the high voltage power supplies 10, 11, 12, 13 were switched off and the system was opened. Under these conditions, an adhesive layer of 10 ⁇ m chromium had previously been deposited in an acetylene-free test.
• Example 2 The same device was used as in Example 1 except that the method described by D. Teer et al. implement proposed improvements.
• the magne- ton sputtering devices at positions 3, 4 and 5 were equipped with target plates made of graphite.
• the workpieces 19, 20 were cleaned as in the previous example, charged and conditioned in argon plasma. After the conditioning step in the argon plasma, an argon pressure of 0.3 Pa was set in the chamber. Thereafter, the high voltage supplies 10, 11, and 12 were turned on and set a current of 6 amps each. Different coating times have been tried. However, layers with a layer thickness of more than 1.5 ⁇ m burst.
• a fourth magnetron sputtering device was added, which was equipped with a target plate made of chromium.
• the procedure up to and including the conditioning again corresponded to that of Example 1.
• an argon pressure of 0.3 Pa was set in the chamber.
• the high voltage power supply 13 was turned on and its current set to 8 amps.
• the high voltage supplies 10, 11, and 12 were turned on and a current of 6 amps each was set. These powers were chosen so that the rotational movements 21 generated by the rotary device movement 7 should deposit multiple layers of about 5 nm thickness of alternating chromium and carbon.
• the component carriers were set into a rotational movement 21 with an increased speed of 10 revolutions / minute compared to Example 1 and the previous experiment, and the component carriers of the cylindrically symmetrical components were additionally set in an autorotation 22.
• a rotational speed of 10 revolutions / minute corresponds to the maximum which can be used with rotary devices 7 according to the prior art.
• An adhesive with rock wave print on a sample of hardened stainless steel showed HF5. However, most of the spalling was observed in the film.
• the layers according to US6726993 have too low tensile strength and ductility, which may be due to their graphitic bonding structure.
• Graphite is known to have a particularly low tensile strength of all materials and is hardly plastically deformable.
• Position 6 was equipped with a cathodic arc evaporator equipped with a carbon target plate.
• power supply 12 a high-power supply KEMPPI 320 was used, as is customary in welding technology.
• Position 5 was equipped with a cathodic arc evaporator equipped with a chromium target plate.
• power supply 13 again a high power KEMPPI 320 was used.
• Positions 3 and 4 were equipped with magnetron sputtering devices equipped with chromium target plates. For the power sources 10 and 11 again high voltage supplies were used. Of course, all other changes necessary to convert cathode sputtering to cathodic arc evaporation were also made.
• the high-frequency insulated high-voltage cables 15 and 16 were replaced by copper cables with 120 mm 2 cross section.
• the arrangement corresponded to JP 2003082458.
• the workpieces were cleaned, charged and conditioned in argon plasma as in the previous example. After the conditioning step in the argon plasma, an argon pressure of 0.3 Pa was set in the chamber.
• the component carriers were set in a rotational movement 21 at a speed of 10 revolutions / minute and the component carrier of the cylindrically symmetrical components were additionally offset in an internal rotation 22.
• the current sources 10 and 11 were turned on and the current was regulated to 8 amps in both. After 5 minutes, nitrogen was admitted into the chamber and the total pressure was increased to 1 Pa with this nitrogen.
• the power source 12 was turned on and set a current of 120 A. An arc was ignited on the cathodic arc evaporator. Thereafter, the nitrogen flow and the two power sources 10 and 11 were turned off. After 45 minutes, the power source 12 was turned off. When the parts were opened, the majority of the carbon layer had broken down, that is, due to cohesive failure, parts of the layer had flaked off. The adhesion of the chromium nitride layer to the substrate and the adhesion of the carbon layer to the chromium nitride layer were satisfactory. The method corresponded to the prior art JP200382458 and WO2005 / 015065.
• WO2005 / 015065 have not yielded a satisfactory result, the prior art methods have been tried with the layering ideas as used in other methods, in particular for CVD methods in US6869676 for PVD methods in US6726993 and for hybrid methods of Strondl et al. in EP1123989 were proposed to combine. Again, a device as in Example 4 was used. However, due to the asymmetry created by the cathodic arc evaporators over the arrangement of Example 2, it was no longer possible to provide a closed magnetic circuit for the unbalanced magnetron sputtering devices. The workpieces were cleaned, charged and conditioned in argon plasma as in the previous example.
• an argon pressure of 0.3 Pa was set in the chamber.
• the component carriers were placed in a rotational movement 21 at a speed of 10 revolutions / minute and the component carriers of the cylindrically symmetrical components were additionally offset in a spin 22.
• the current sources 10 and 11 were turned on and the current was regulated to 8 amps in both.
• the power source 14 was turned on and a current of 120 A was set.
• An arc was ignited on the cathodic arc evaporator 6.
• the power sources 11, 12 and 14 were turned off.
• the parts had been coated with a layer of 7 ⁇ m. There were no spontaneous flaking. In the adhesion test, however, cohesive flaking was noted.
• Example 7 Again, a device as in Example 4 was used. The workpieces and components were cleaned, charged and conditioned in argon plasma as in previous examples. After the conditioning step in the argon plasma, an argon pressure of 0.3 Pa was set in the chamber. The component carriers were set in a rotational movement 21 at a speed of 10 revolutions / minute, and the component carriers of the cylindrically symmetrical components were additionally set in an autorotation 22. The current source 13 was turned on, the current was set to 85 amps. Thereafter, an arc was ignited on the cathodic arc evaporator 5 and carried out a metal plasma conditioning, as known from the prior art.
• the current of current source 13 was increased to 120 amps and a chrome plating was initiated by lowering the workpiece bias. Thereafter, the current sources 10 and 11 were turned on and the current was regulated at both to 6 amps. After 3 minutes, the power source 14 was turned on and a current of 120 A was set. On the cathodic arc evaporator 6, an arc was ignited. After 35 minutes, the power sources 11, 12, 13 and 14 were turned off. The parts had been coated with a layer of 8 ⁇ m. There were no spontaneous flaking. In the adhesion test, however, cohesive flaking was noted. Calotte slices were made and examined.
• the layer had a multilayer structure with carbon lamellae of less than 2 nm thickness up to 8 nm alternating with 20 nm thick chromium layers.
• the calotte finish showed why these layers fail in the adhesion test.
• the chromium layers burst from the carbon layers in many places. Compared to Example 5 but a noticeable improvement was found.
• Example 8 Again, a device as in Example 5 was used. The workpieces were cleaned, charged and conditioned in argon plasma as in previous examples. After the conditioning step in the argon plasma, an argon pressure of 0.3 Pa was set in the chamber. The component carriers were set in a rotational movement 21 at a speed of 10 revolutions / minute and the component carriers of the cylindrically symmetrical components were additionally set in an autorotation 22. The current source 13 was turned on, the current was set to 85 amps. Thereafter, an arc was ignited on the cathodic arc evaporator 5 and carried out a metal plasma conditioning, as known from the prior art.
• the current of current source 13 was increased to 150 amps and a chrome coating was started by lowering the workpiece bias. After 3 minutes, the power source 14 was turned on and a current of 100 A was set. On the cathodic arc evaporator 6, an arc was ignited. After 45 minutes, the current sources 13 and 14 were turned off. The parts had been coated with a layer of 7.5 ⁇ m. There were no spontaneous flaking. In the adhesion test, however, cohesive flaking was noted. Calotte slices were made and examined. The layer had a multilayer structure with carbon lamellae less than 2 nm thick up to 6 nm alternating with 10 nm thick chrome lamination layers. The calotte grinding is shown in Figure 4. He shows why these layers fail in the adhesion test. The chromium layers 34 burst from the carbon layers 33 at a plurality of locations 37. Compared to the layers of Example 7 but a noticeable improvement was found.
• Example 9 Example 9:
• the plant used in the previous examples was rebuilt.
• the magnetron sputtering devices 3 and 4 were removed. So that the system was equipped only with the two cathodic arc evaporators 5 and 6 on the positions shown in Figure 1.
• the cathodic arc evaporator 6 was equipped with a carbon target
• the cathodic arc evaporator 5 with a chrome target.
• the rotary device and the component carrier 9 were replaced by a new construction as follows: The rotary device allowed a rotational speed of 100 revolutions / minute. To achieve this, a new powerful engine with a corresponding gear was used. All other assemblies were also redesigned: All plain bearings were replaced by ball bearings.
• the substrate power supply was disconnected from the motion supply and the electrical contact was made directly to the substrate receiving spindles.
• the plug-in connections to the substrate receptacles were replaced by screw connections or, preferably, form-fitting connections. All components that were exposed to the centrifugal forces have been reinforced compared to the prior art.
• the workpieces used were precision ground martensitic stainless steel discs and hardened steel piston ring portions and bushings 20 of aluminum alloy common to these components. These were cleaned with an industrial cleaning method according to the prior art and fixed to the workpiece and component carrier 9.
• the chamber was pumped to a pressure of 4 mPa.
• the component carriers were placed in a rotation movement 21 at a speed of 100 revolutions / minute and the component carriers of the cylindrically symmetrical components were additionally set in an autorotation 22.
• an argon pressure of 0.3 Pa was set in the chamber.
• the current source 13 was turned on, the current was set to 85 amps. Thereafter, an arc was ignited on the cathodic arc evaporator 5 and a metal plasma conditioning, as known from the prior art, performed.
• the Current of the current source 13 is increased to 150 amps and started by lowering the workpiece bias a chrome plating.
• the power source 14 was turned on and a current of 100 A was set.
• Example 9 The plant was rebuilt again.
• the cathodic arc evaporator equipped with the chrome target was moved from position 5 to position 3. Wiring and cooling water supply have been changed accordingly. Thereafter, a coating was carried out as in Example 9.
• the parts had been coated with a layer of 8 ⁇ m. There were no spontaneous flaking.
• Calotte cuts and cross sections for transmission electron microscopy were made and examined.
• the transmission electron micrograph is reproduced as FIG. FIG. 5 shows that the layer has no multilayer structure. There are no carbon layers and chrome layers visible. However, you still can Recognize a composition modulation 39 with a frequency of 2 nm. This corresponds to a layer deposited during one revolution.
• the calotte grinding is shown in FIG. You can not see a single local flaking.
• Figure 7 shows that the layers consist essentially of chromium carbide whose grain size is in the nm range, and amorphous carbon.
• the grain size varies irregularly in the course of the shift.
• the layers contain no detectable metallic chromium.
• a multi-layered structure is still partially present, but there are no longer continuous carbon louvers.
• the layer has portions 38 in which the structure is nearly isotropic, that is, chromium carbide grains and carbon particles.
• the size of the chromium carbide grains is in the range of 1 to 5 nm. It is also crucial that the carbon lamellae of carbide grains 39 are also interspersed in the region of the layer in which a multilayer structure still exists. The absence of continuous carbon lamellae probably results in excellent tribological properties.
• Friction coefficient and wear rate measurement were performed on the coated wheels. Both measurements were carried out with a sintered alumina ball. A coefficient of sliding friction of 0.22 was measured. The wear rate was 3 ⁇ 10 -17 m 3 / Nm.
• Example 11 The construction of the plant was the same as in Example 10.
• the coating process was also the same as in Example 10. However, 3 minutes after ignition of the arc on the arc evaporator 6, nitrogen was introduced into the plant namely 160 sccm. The coating was then continued for 50 minutes with constant parameter setting. Upon opening, it was found that the parts were coated with a layer of 10 microns. There were no spontaneous flaking. The transmission electron micrograph showed that the layer has no multilayer structure. There were no carbon layers and chrome layers recognizable. However, one can still see a composition modulation with a frequency of 2 nm. This corresponds to a layer deposited during one revolution. In the Kalottenschliff you could not detect a single local flaking.
• Friction coefficient and wear rate measurement were performed on the coated wheels. Both measurements were carried out with a sintered alumina ball. A coefficient of sliding friction of 0.20 was measured. The wear rate was 1.2 ⁇ 10 -17 m 3 / Nm.
• the cathodic arc evaporation device 6 was rebuilt.
• the magnetic guidance of the cathode footpoint has been changed.
• the magnetic guidance of the cathode footpoint of Examples 4-11 is described in Figure 8a.
• the magnetic guide of the cathode foot of Examples 4-11 had consisted of magnetic lines 39 whose vertices formed 3 rings 41.
• the unillustrated magnetic field generating device rotated about an axis normal to the target plate, causing the rings to orbit the target plate center.
• the cathode footpoint of a web 40 has followed, which has repeatedly left the imprinted leadership and has slowly changed from one ring to another. This magnetic field has now been replaced by a simpler one, shown in Figure 8b.
• the vertex Points of the lines 42 of this magnetic field form a circle.
• This magnetic field has numerous disadvantages compared with the magnetic field 8a, which will not be discussed in detail here. But, the cathode foot point performs a much faster and, above all, even circular meandering movement 43.
• the other assemblies were left unchanged from Example 11.
• the coating process was carried out as in Example 11 and 10 ⁇ m of layer were again deposited. Calotte cuts and cross sections for transmission electron microscopy were made and examined. The result of transmission electron microscopy is reproduced as a dark field image in FIG.
• the structure of the layer corresponded to that of Examples 10 and 11. But the grain size varied regularly in the course of the layer.
• This grain size variation can be observed in the dark field image taken with the chromium carbide line as "Milky Way Lanes" 44.
• a layer with a larger particle size corresponds to one "Milky Way”.
• the frequency of the grain size layers corresponds to the frequency of Kathodenfussticianrotation. It is believed that depending on the position of the cathode root point to the parts, the crystallite size of the deposited layer is larger or smaller. Whether the distance of the Katodenfussticians from the component surface or the angle between the connecting line from the cathode foot to the component surface and the normal to the target surface is the decisive parameter could not be determined with our device. Nor could it be determined whether the coarser grains corresponded to a shorter or longer distance. Friction coefficient and wear rate measurement were performed on the coated wheels. Both measurements were carried out with a sintered alumina ball. A coefficient of sliding friction of 0.18 was measured. The wear rate was 2 ⁇ 10 -18 m 3 / Nm.
• the choice of the metal or the alloy will be oriented by the person skilled in the art to the conditions of use of the component.
• carbide layers and layers of sulfides silicides and borides are conceivable.
• sulfur, silicon and boron would be embedded.
• the periodic variation of the concentration of the metalloid and the metals in some cases facilitates the formation of compound crystals and prevents the deposition of amorphous layers.
• a variation with a period of 2 nm has proven to be useful.
• the addition of nitrogen, which is likely to be in the form of a carbonitride, to the gas atmosphere in which the coating is carried out has also been proven. To ensure a low coefficient of friction, the nitrogen content of the layer should not exceed the carbon content.
• the composition of the layer is determined by the ratio of the evaporator streams in the preferred method of Kolfbogenverdampfung for their preparation. In other methods, such as sputtering, one would use the target performance for composition optimization.
• the optimal composition should be within a certain range. Details depend on the area of application of the component and the carbide formation during the coating. The latter can be controlled, for example, in the system chromium-carbon by the coating temperature and the workpiece preload during the coating process. A lower range of 20, preferably 40 atomic percent carbon should not be undercut to T / CH2007 / 000167
• Wear protection layers according to the prior art were generally thin, 1-3 ⁇ m. Our experiments have shown that such thin layers are unsuitable for component wear protection, as they are rubbed too quickly at the roughness peaks. The prior art used such thin layers because the layers have insufficient mechanical properties. The last example has shown that a periodic variation of the grain size has a particularly advantageous effect on the wear rate.
• the reactive co-evaporation process we invented can be applied to all materials consisting of compounds whose components can be vaporized by physical methods. It is naturally suitable for the deposition of carbides, bonding sulphides and silicides of the metals, but also more exotic compounds such as tellurides may be presentable by this process.
• An essential characteristic of the method according to the invention is that the workpieces and components are exposed simultaneously or at very short intervals to the vapor of a physical metal source and a physical metalloid source. This is achieved in that the two physical vapor sources are arranged at a certain distance from each other, which of course also depends on the distance of the functional surfaces to be coated of the workpieces and components of the surfaces of the two sources. A maximum distance of 150 mm should only be exceeded if it is compensated by other plant engineering measures.
• cathodic arc evaporators have proven particularly useful.
• the studied example of the combination
• Chromium / carbon the co-use of magnetron cathode sputtering devices for the production of carbon vapor had a negative effect on the mechanical properties of the layers. On the other hand improved in this
• the use of a nitrogen-containing atmosphere has the layer properties, while the use of a hydrocarbon-containing atmosphere has degraded the layer properties.
• a further improvement of the carbonaceous component wear protection coating has been achieved by guiding the functional surfaces of the components at fairly rapid intervals in the vicinity of the cathode footprint on the carbon target. This is achieved by a special guidance of the cathode foot of the carbon evaporating arc evaporator.
• the illustrated but not exclusive example uses a strong magnetic field forming an elliptical channel. A particular embodiment of the ellipse is the circle.
• the oscillatory motion normal to the axis of rotation is the projection of the path of cathode footing 43 onto the diagonal of the target plate which is normal to the axis of the turntable movement.
• the time period of the oscillatory motion should, however, be much larger than the period in the functional surface is moved from one physical vapor source to the next. A period of 1 - 6 seconds has been proven.

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• 2007
  • 2007-04-02 EP EP07720066A patent/EP2007922A2/de not_active Withdrawn
  • 2007-04-02 JP JP2009503387A patent/JP2009532581A/ja not_active Withdrawn
  • 2007-04-02 WO PCT/CH2007/000167 patent/WO2007115419A2/de not_active Ceased

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