WO2023275109A1 - Élément métallique doté de revêtement de protection contre l'usure - Google Patents

Élément métallique doté de revêtement de protection contre l'usure Download PDF

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Publication number
WO2023275109A1
WO2023275109A1 PCT/EP2022/067827 EP2022067827W WO2023275109A1 WO 2023275109 A1 WO2023275109 A1 WO 2023275109A1 EP 2022067827 W EP2022067827 W EP 2022067827W WO 2023275109 A1 WO2023275109 A1 WO 2023275109A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal component
layer
metal
wear
tungsten
Prior art date
Application number
PCT/EP2022/067827
Other languages
German (de)
English (en)
Inventor
Bernhard Mandl
Stefan BEIRLE
Peter OBERHUMER
Jens Emmerlich
Original Assignee
Robert Bosch Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO2023275109A1 publication Critical patent/WO2023275109A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/024Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025Metallic sublayers
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641Nitrides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02MSUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M2200/00Details of fuel-injection apparatus, not otherwise provided for
    • F02M2200/02Fuel-injection apparatus having means for reducing wear
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02MSUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M2200/00Details of fuel-injection apparatus, not otherwise provided for
    • F02M2200/90Selection of particular materials
    • F02M2200/9038Coatings

Definitions

  • the invention relates to a metal component with a wear protection coating, in particular a hydraulic valve component, the tribologically stressed surface of which is at least partially provided with a wear protection layer which is applied to an adhesive layer arranged between the metal component and the wear protection layer.
  • the invention relates, as an exemplary application, to a hydraulic valve that is equipped with such a metal component with a wear protection coating, and to a method for applying at least one wear protection layer to the metal component.
  • the field of application of the invention extends primarily to tribologically highly stressed components, preferably in motor vehicle technology.
  • Functional layers for surface finishing are primarily used to protect against wear and represent a widespread means of increasing long-term resilience.
  • the hard material layers of interest are used, which preferably consist of metal nitrides or metal carbides.
  • components such as hydraulic high-pressure components are subject to high local stresses while maintaining very small dimensional tolerances.
  • valve or high-pressure pump components in fuel injection systems are protected from wear with such hard material layers.
  • reliable layer adhesion of the at least one wear protection layer must be ensured. State of the art
  • DE 102018202 842 A1 discloses a generic anti-wear coated metal component.
  • a tribologically stressed surface of the metal component is at least partially provided with a multi-layer wear protection layer which, in the terminology of the disclosure, has at least one metallic bonding layer, one bonding agent layer and at least one top layer.
  • the metallic adhesion layer consists of a metal
  • the adhesion promoter layer applied thereon consists of a hydrogen-free carbide-forming metal or a boride-forming metal.
  • the top layer applied to this consists of a hydrogen-free tetrahedral carbon. This layer structure causes a thermally stable adhesion of the individual layers to one another, which means that a high level of resistance to high tribological loads is achieved.
  • the layers are bonded by applying the coating directly to the component surface. Diffusion of metals originating from the metal component, such as in particular iron, chromium, nickel or molybdenum, and non-metals originating therefrom, such as nitrogen or carbon, can impair the adhesion of layers, in particular wear protection layers made of metal carbides or metal nitrides.
  • the tendency of the aforementioned non-metals to diffuse is caused in particular by the surface hardening of a metal component made of chromium-nickel, chromium-molybdenum or chromium-nickel-molybdenum steel, in that carbon or nitrogen is introduced into the surface of the metal component during carburizing or nitriding .
  • a metal component made of chromium-nickel, chromium-molybdenum or chromium-nickel-molybdenum steel, in that carbon or nitrogen is introduced into the surface of the metal component during carburizing or nitriding .
  • heavy elements such as the iron in the base material or chromium as an alloy can also diffuse into the coating.
  • Claim 9 specifies an associated manufacturing method for applying a wear protection layer to a tribologically highly stressed metal component and claim 11 relates to the use of tungsten or a tungsten compound for the purpose of the invention.
  • the invention includes the technical teaching that a diffusion barrier layer consisting of tungsten W or a tungsten compound is arranged between the metal component and an adhesive layer bearing an anti-wear layer, which layer blocks the diffusion of metals originating from the metal component - in particular iron, chromium, nickel, molybdenum and the resulting non-metals - especially nitrogen and carbon - are absorbed or blocked so that the latter cannot penetrate to the adhesive layer.
  • a diffusion barrier layer consisting of tungsten W or a tungsten compound is arranged between the metal component and an adhesive layer bearing an anti-wear layer, which layer blocks the diffusion of metals originating from the metal component - in particular iron, chromium, nickel, molybdenum and the resulting non-metals - especially nitrogen and carbon - are absorbed or blocked so that the latter cannot penetrate to the adhesive layer.
  • the solution according to the invention ensures a barrier defined within the specific layer structure in order to prevent a diffusion of light elements—particularly carbon and nitrogen—and/or heavy elements—particularly iron, chromium, nickel, molybdenum.
  • the advantage of the solution according to the invention is in particular that, thanks to the diffusion barrier layer specially integrated into the layer structure, a conversion of parts of the adhesive layer and the wear protection layer as a result of diffusion of the aforementioned elements is prevented.
  • the diffusion barrier layer preferably consists of tungsten carbide or alternatively tungsten nitride.
  • tungsten carbide in particular leads to exceptionally high layer adhesion.
  • a high-alloy chromium-nickel, chromium-molybdenum or chromium-nickel-molybdenum steel is preferably used as the metal component to be coated.
  • These steel alloys are mostly used for tribologically highly stressed components of the type of interest here and are usually surface-hardened by means of carburizing or, in particular, nitriding.
  • the diffusion barrier layer according to the invention effectively prevents the carbon or nitrogen thus introduced into the surface of the metal component from diffusing, in that these elements are absorbed by the diffusion barrier layer so that they do not penetrate to the subsequent adhesive layer.
  • the diffusion barrier layer consisting of tungsten W or one of the said tungsten compounds directly blocks the diffusion of metals originating from the steel component, here in particular iron and chromium.
  • the anti-wear layer used in the layer structure according to the invention is preferably designed as a metal carbide or metal nitride compound selected from a group comprising: chromium nitride, aluminum chromium nitride, aluminum chromium titanium nitride, aluminum titanium nitride, chromium carbide, titanium nitride, titanium carbonitride.
  • metal carbide or metal nitride compound selected from a group comprising: chromium nitride, aluminum chromium nitride, aluminum chromium titanium nitride, aluminum titanium nitride, chromium carbide, titanium nitride, titanium carbonitride.
  • an adhesive layer is preferably used between the wear protection layer and the metal component, which according to a preferred embodiment is designed as a high-purity transition metal layer selected from a group of transition metals, including chromium, titanium, molybdenum, vanadium, hafnium, tantalum, zirconium or combinations thereof.
  • the adhesive layer should be formed with a layer thickness between 0.05 to 1 micron, on the one hand by the minimum thickness to carry out a reliable adhesion promoter function and on the other hand to realize a relatively thin coating at maximum thickness.
  • a layer thickness of between 0.01 and 1 micron is recommended for the diffusion barrier layer.
  • the absorption capacity of the non-metals diffusing in here increases with increasing layer thickness; on the other hand, reliable protection is already achieved from the minimum layer thickness.
  • a layer thickness beyond the maximum specification does not lead to a significant improvement in the barrier function.
  • the layer structure described above can preferably be achieved by the following coating steps:
  • a diffusion barrier layer consisting of tungsten W or a tungsten compound to the surface of the metal component to be coated
  • an adhesion layer consisting in particular of a transition metal
  • At least one anti-wear layer consisting in particular of a metal-carbide or metal-nitride compound.
  • the known vacuum-assisted and plasma-activated PVD process techniques are suitable for applying the tribological hard material layer in the form of the wear protection layer and also for applying the intermediate layers that are the subject of the invention, so that the layer structure can be realized in an efficient manner in terms of production technology.
  • a metallic top layer can be applied over a wear protection layer in order to reduce the mechanical stress on the layer structure.
  • FIG. 1 shows a schematic longitudinal section through a hydraulic valve comprising a metal component with a wear protection coating
  • FIG. 2 shows a detailed sectional view of a metal component with a wear-resistant layer coating according to the invention.
  • a hydraulic valve 10 designed as a ball valve comprises a metal component 1 with a wear protection coating, which forms a conical valve seat 11 here.
  • the valve seat 11 interacts with a spherical counter-body 12, which can be brought into contact with the valve seat 11 in a generally known manner in order to close the valve.
  • the metal component 1 with a wear protection coating is provided with a multilayer coating 3 for wear protection in the area of the tribologically stressed surface 2 .
  • this multilayer coating 3 consists in detail of an outer wear protection layer 4, which in this exemplary embodiment consists of chromium nitride applied by deposition in a PVD process.
  • This wear-protection layer 4 is applied to an adhesive layer 5, which in this exemplary embodiment consists of chromium deposited using the PVD method and serves to improve layer adhesion and thus functions as a highly pure transition metal layer.
  • a chrome top layer can be applied.
  • the metal component 1 consists here of a high-alloy chromium-nickel-molybdenum steel, namely X40CrMoV5-1, which is surface-hardened by nitriding.
  • the diffusion barrier layer 6 not only prevents diffusion of the metal component 1 contained by the nitriding
  • the solution according to the invention enables a double diffusion barrier layer to achieve a particularly stable adhesion of the layer

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un élément métallique (1) comportant un revêtement de protection contre l'usure, en particulier un élément soupape hydraulique, dont la surface à charge tribologique (2) est munie, au moins en partie, d'un revêtement de protection contre l'usure (4) disposé sur une couche adhésive (5) disposée entre l'élément métallique (1) et la couche de protection contre l'usure (4). Une couche barrière de diffusion (6), constituée de tungstène (W) ou d'un composé de tungstène, est disposée entre l'élément métallique (1) et la couche adhésive (5), afin de bloquer la diffusion de métaux (Fe, Cr, Ni, Mo) issus de l'élément métallique (1) et d'absorber ou de bloquer des non-métaux (N, C) issus dudit élément, de sorte que ces derniers ne pénètrent pas dans la couche adhésive (5).
PCT/EP2022/067827 2021-06-29 2022-06-29 Élément métallique doté de revêtement de protection contre l'usure WO2023275109A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021206765.4 2021-06-29
DE102021206765.4A DE102021206765A1 (de) 2021-06-29 2021-06-29 Verschleißschutzbeschichtetes Metallbauteil

Publications (1)

Publication Number Publication Date
WO2023275109A1 true WO2023275109A1 (fr) 2023-01-05

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DE (1) DE102021206765A1 (fr)
WO (1) WO2023275109A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10038954A1 (de) * 2000-08-09 2002-02-28 Siemens Ag Ventil, insbesondere Einspritzventil
DE102018202842A1 (de) 2018-02-26 2019-08-29 Robert Bosch Gmbh Verschleißschutzbeschichtetes metallisches Bauteil insbesondere für ein Kugelventil und Verfahren zum Aufbringen einer mehrschichtigen Verschleißschutzschicht zur Erzeugung eines solchen Bauteils
DE102018125631A1 (de) * 2018-10-16 2020-04-16 Schaeffler Technologies AG & Co. KG Schichtsystem, Rollelement und Verfahren

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10038954A1 (de) * 2000-08-09 2002-02-28 Siemens Ag Ventil, insbesondere Einspritzventil
DE102018202842A1 (de) 2018-02-26 2019-08-29 Robert Bosch Gmbh Verschleißschutzbeschichtetes metallisches Bauteil insbesondere für ein Kugelventil und Verfahren zum Aufbringen einer mehrschichtigen Verschleißschutzschicht zur Erzeugung eines solchen Bauteils
DE102018125631A1 (de) * 2018-10-16 2020-04-16 Schaeffler Technologies AG & Co. KG Schichtsystem, Rollelement und Verfahren

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