WO2010012701A1 - Anti-wear layer system and component comprising an anti-wear layer arrangement - Google Patents

Anti-wear layer system and component comprising an anti-wear layer arrangement Download PDF

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Publication number
WO2010012701A1
WO2010012701A1 PCT/EP2009/059696 EP2009059696W WO2010012701A1 WO 2010012701 A1 WO2010012701 A1 WO 2010012701A1 EP 2009059696 W EP2009059696 W EP 2009059696W WO 2010012701 A1 WO2010012701 A1 WO 2010012701A1
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WO
WIPO (PCT)
Prior art keywords
layer
adhesion promoter
wear protection
component
protection layer
Prior art date
Application number
PCT/EP2009/059696
Other languages
German (de)
French (fr)
Inventor
Kurt Burger
Ronald Neidhardt
Klaus Burghoff
Rainer Feuerfeil
Guenter Schneider
Ulrich May
Original Assignee
Robert Bosch Gmbh
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Publication of WO2010012701A1 publication Critical patent/WO2010012701A1/en

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    • 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
    • C23C14/22—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
    • 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
    • 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
    • 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
    • C23C28/048—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 with layers graded in composition or physical properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M59/00—Pumps specially adapted for fuel-injection and not provided for in groups F02M39/00 -F02M57/00, e.g. rotary cylinder-block type of pumps
    • F02M59/44—Details, components parts, or accessories not provided for in, or of interest apart from, the apparatus of groups F02M59/02 - F02M59/42; Pumps having transducers, e.g. to measure displacement of pump rack or piston
    • F02M59/445—Selection of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M61/00—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00
    • F02M61/04—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00 having valves, e.g. having a plurality of valves in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M61/00—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00
    • F02M61/16—Details not provided for in, or of interest apart from, the apparatus of groups F02M61/02 - F02M61/14
    • F02M61/166—Selection of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B1/00—Multi-cylinder machines or pumps characterised by number or arrangement of cylinders
    • F04B1/04—Multi-cylinder machines or pumps characterised by number or arrangement of cylinders having cylinders in star- or fan-arrangement
    • F04B1/0404—Details or component parts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M2200/00—Details of fuel-injection apparatus, not otherwise provided for
    • F02M2200/90—Selection of particular materials
    • F02M2200/9038—Coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M2200/00—Details of fuel-injection apparatus, not otherwise provided for
    • F02M2200/90—Selection of particular materials
    • F02M2200/9046—Multi-layered materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2253/00—Other material characteristics; Treatment of material
    • F05C2253/12—Coating

Definitions

  • the invention relates to a wear protection layer arrangement, in particular for components exposed to high pressures and temperatures of a fuel injection system, according to the preamble of claim 1 and to a component according to claim 9.
  • a metal-free, amorphous, hydrogen-containing carbon layer (a-C: H layer) is used by the applicant as a wear protection layer to reduce friction and wear as standard.
  • the thickness of the carbon layer applied to the component surface by plasma-technological processes is between 1 ⁇ m and 3 ⁇ m.
  • ta-C layer tetragonal amorphous, hydrogen-free carbon layers
  • H layers aC: H layers.
  • the ta-C layer is provided as part of a wear protection layer arrangement which, in addition to the ta-C layer, has an adhesion promoter layer of plasma supported on deposited titanium.
  • the known wear protection layer arrangement has proven itself. However, there are, especially with regard to to the increasing pressures in injection technology, efforts to improve the adhesion of ta-C coatings on component surfaces.
  • DE 10 2005 062 204 A1 discloses a wear protection coating for printing press elements exposed to low pressures in comparison with injection system components.
  • This comprises a protective layer of tetragonal bonded amorphous carbon, wherein a chromium layer is arranged as adhesion promoter layer between the surface of a substrate to be coated and the carbon protective layer.
  • the known protective layer arrangement is not suitable for the harsh ambient parameters occurring in fuel injection systems of pressures above 2000 bar and temperatures around 400 ° C.
  • the invention has the object to provide a particularly durable protective layer arrangement. This should preferably withstand test conditions under an inert gas atmosphere at 400 ° C for a period of 150 hours, at least largely, without damage. Furthermore, the object is to propose a coated with a corresponding protective layer device, in particular a fuel injection system.
  • the invention is based on the idea, in addition to a first adhesion promoter layer of pure chromium or at least with a chromium portion, to provide a second adhesion promoter layer which contains a carbon content.
  • a first adhesion promoter layer of pure chromium or at least with a chromium portion to provide a second adhesion promoter layer which contains a carbon content.
  • the protective layer with tetragonal bonded, amorphous carbon is preferably hydrogen-free.
  • an improved temperature resistance in test tests under an inert gas atmosphere at a temperature of about 400 0 C over a period of 150 hours can be achieved.
  • the second adhesion promoter layer has a chromium content in addition to the carbon content.
  • the second adhesion promoter layer is preferably designed as a mixed layer comprising carbon components and chromium components.
  • the second adhesion promoter layer is formed as a so-called gradient layer with at least two locations different chromium / carbon ratio.
  • the carbon content increases with increasing layer thickness in the direction of the protective layer, preferably linear.
  • the wear protection layer arrangement in which the protective layer of tetragonal bonded amorphous carbon is applied directly to the second adhesion promoter layer.
  • the protective layer particularly preferably forms an outer layer of the wear protection layer arrangement, that is to say a cover layer which comes into direct contact with operating media, for example fuel.
  • the first adhesion promoter layer and / or the second adhesion promoter layer have / has a layer thickness of a value range between approximately 50 nm and approximately 300 nm.
  • the total thickness of the wear layer arrangement is selected from a value range between about 1 ⁇ m and 10 ⁇ m.
  • the first adhesion promoter layer by means of a PVD process (physical vapor deposition) directly onto the surface of the first component to be coated, preferably at least in the region of steel to be coated.
  • a PVD process physical vapor deposition
  • this is sputtered a chromium target, in which this is bombarded with inert argon ions.
  • the protective layer is applied by means of a PVD process, preferably under vacuum, most preferably by arc vapor deposition (Arc-PVD).
  • the second adhesion promoter layer as a mixed layer comprising o- is formed consisting of chromium and carbon
  • acetylene gas ethyne
  • the proportion of carbon can be increased with increasing layer thickness.
  • the invention also leads to a component, in particular a fuel injection system.
  • the device at least in the area to be coated, made of steel.
  • the device is characterized by a trained according to the concept of the invention, previously described wear protection layer arrangement.
  • the component is very particularly preferably a component of a fuel injector, in particular a nozzle needle, which is preferably provided with a wear protection layer arrangement at least in the seating area.
  • the component may be a component of a high-pressure fuel pump, preferably a pump blade exposed to heavy loads.
  • FIG. 1 is a coated with a three-layer wear protection layer assembly of steel component of a fuel injection system.
  • a coated with a wear protection layer assembly 1 component B made of steel is shown.
  • the component B is a component of an injection system, preferably a nozzle needle tip of a fuel injector or a pump impeller, of a high-pressure fuel pump for supplying a high-pressure fuel accumulator (rail).
  • the wear protection layer assembly 1 is applied directly to an outer surface O of the component B.
  • the wear protection layer arrangement 1 comprises a first adhesion promoter layer
  • this first adhesion promoter layer 2 is from a value range between approximately
  • the first adhesion promoter layer 2 is applied to the surface O by means of a PVD process comprising bombarding a chromium target with argon ions.
  • a second adhesion promoter layer 3 Immediately adjoining the first adhesion promoter layer 2 is a second adhesion promoter layer 3. This is formed as a mixed layer comprising the components chromium and carbon. In this case, the carbon content of the second adhesion promoter layer formed as a gradient layer increases
  • the second adhesive layer 3 starting from the first bonding agent layer 2 in the direction of the drawing plane upwards, ie with increasing layer thickness.
  • the second adhesive layer 3 has likewise a layer thickness from a value range between about 50 nm and about 300 nm.
  • a combined PVD / CVD method is used, wherein acetylene gas is fed to the argon ions for sputtering a chromium target.
  • the protective layer 4 serving as a cover layer. This consists of tetragonal bonded, amorphous, hydrogen-free carbon.
  • the protective layer 4 is applied to the second adhesion promoter layer 3 by means of a PVD process in which carbon evaporates by means of a vacuum arc.
  • the anti-wear layer arrangement 1 shown in FIG. 1 and applied to the component B has a particularly good adhesive strength and temperature resistance.
  • the wear protection layer arrangement 1 is temperature-resistant in a test method in which the coated component B is exposed to an inert gas atmosphere for 150 hours at a temperature of about 400 0 C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel-Injection Apparatus (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention relates to an anti-wear layer arrangement (1), especially for components (B) of a fuel injection system, which are exposed to high pressures and temperatures. Said arrangement comprises a protective layer (4) formed from an amorphous tetragonally bound carbon or comprising a part of amorphous tetragonally bound carbon, and a first adhesive layer (2) formed from chromium or comprising a chromium part. According to the invention, at least one second adhesive layer (3) comprising a carbon part is provided adjacent to the first adhesive layer (2). The invention also relates to a component (B).

Description

Beschreibungdescription
Titeltitle
Verschleißschutzschichtanordnung sowie Bauelement mit Ver- SchleißschutzschichtanordnungWear protection layer arrangement and component with wear protection layer arrangement
Stand der TechnikState of the art
Die Erfindung betrifft eine Verschleißschutzschichtanord- nung, insbesondere für hohen Drücken und Temperaturen ausgesetzte Bauelemente eines Kraftstoffeinspritzsystems, gemäß dem Oberbegriff des Anspruchs 1 sowie ein Bauelement gemäß Anspruch 9.The invention relates to a wear protection layer arrangement, in particular for components exposed to high pressures and temperatures of a fuel injection system, according to the preamble of claim 1 and to a component according to claim 9.
Bei Bauelementen in der Dieseleinspritztechnik wird serienmäßig von der Anmelderin seit etwa 1997 eine metallfreie, amorphe, wasserstoffhaltige KohlenstoffSchicht (a-C:H- Schicht) als Verschleißschutzschicht zur Minderung von Reibung und Verschleiß eingesetzt. Die Dicke der durch plasma- technische Verfahren auf der Bauelementoberfläche aufgetragenen KohlenstoffSchicht beträgt zwischen lμm und 3μm.For components in the diesel injection technology, since about 1997, a metal-free, amorphous, hydrogen-containing carbon layer (a-C: H layer) is used by the applicant as a wear protection layer to reduce friction and wear as standard. The thickness of the carbon layer applied to the component surface by plasma-technological processes is between 1 μm and 3 μm.
Seit September 2006 werden auf Bauelementen von Dieseleinspritzsystemen tetragonal amorphe, wasserstofffreie Kohlen- stoffschichten (ta-C-Schicht) eingesetzt, die sich gegenüber den a-C : H-Schichten durch verbesserte Eigenschaften auszeichnen. Um die ta-C-Schicht haftfest auf das Bauelement aufbringen zu können, wird die ta-C-Schicht als Bestandteil einer Verschleißschutzschichtanordnung vorgese- hen, die zusätzlich zu der ta-C-Schicht eine Haftvermittlerschicht aus Plasma unterstützt abgeschiedenem Titan aufweist. Die bekannte Verschleißschutzschichtanordnung hat sich bewährt. Es bestehen jedoch, insbesondere im Hinblick auf die in der Einspritztechnologie immer weiter steigenden Drücke, Bestrebungen die Haftfestigkeit von ta-C-Schichten auf Bauelementoberflächen zu verbessern.Since September 2006, components of diesel injection systems have been using tetragonal amorphous, hydrogen-free carbon layers (ta-C layer), which have improved properties compared to the aC: H layers. In order to be able to firmly adhere the ta-C layer to the component, the ta-C layer is provided as part of a wear protection layer arrangement which, in addition to the ta-C layer, has an adhesion promoter layer of plasma supported on deposited titanium. The known wear protection layer arrangement has proven itself. However, there are, especially with regard to to the increasing pressures in injection technology, efforts to improve the adhesion of ta-C coatings on component surfaces.
Aus der DE 10 2005 062 204 Al ist eine Verschleißschutzbe- schichtung für im Vergleich zu Einspritzsystembauelementen geringen Drücken ausgesetzten Druckmaschinenelemente bekannt. Diese umfasst eine Schutzschicht aus tetragonal gebundenem amorphem Kohlenstoff, wobei zwischen der Oberflä- che eines zu beschichtenden Substrates und der Kohlenstoff- Schutzschicht eine Chromschicht als Haftvermittlerschicht angeordnet ist. Die bekannte Schutzschichtanordnung ist nicht für die rauen, in Kraftstoffeinspritzsystemen auftretenden Umgebungsparametern von Drücken über 2000 bar und Temperaturen um 4000C geeignet.DE 10 2005 062 204 A1 discloses a wear protection coating for printing press elements exposed to low pressures in comparison with injection system components. This comprises a protective layer of tetragonal bonded amorphous carbon, wherein a chromium layer is arranged as adhesion promoter layer between the surface of a substrate to be coated and the carbon protective layer. The known protective layer arrangement is not suitable for the harsh ambient parameters occurring in fuel injection systems of pressures above 2000 bar and temperatures around 400 ° C.
Offenbarung der Erfindung Technische AufgabeDISCLOSURE OF THE INVENTION Technical Problem
Der Erfindung liegt die Aufgabe zugrunde, eine besonders haltbare Schutzschichtanordnung vorzuschlagen. Diese sollte bevorzugt Prüfbedingungen unter einer inerten Gasatmosphäre bei 400°C über einen Zeitraum von 150 Stunden, zumindest weitgehend, beschädigungsfrei überstehen. Ferner besteht die Aufgabe darin, ein mit einer entsprechenden Schutzschichtanordnung beschichtetes Bauelement, insbesondere eines Kraftstoff-Einspritzsystems vorzuschlagen.The invention has the object to provide a particularly durable protective layer arrangement. This should preferably withstand test conditions under an inert gas atmosphere at 400 ° C for a period of 150 hours, at least largely, without damage. Furthermore, the object is to propose a coated with a corresponding protective layer device, in particular a fuel injection system.
Technische LösungTechnical solution
Diese Aufgabe wird hinsichtlich der Schutzschichtanordnung mit dem Merkmal des Anspruchs 1 und hinsichtlich des Bauelementes mit den Merkmalen des Anspruchs 9 gelöst. Vor- teilhafte Weiterbildungen der Erfindung sind in den Unteransprüchen angegeben. In den Rahmen der Erfindung fallen sämtliche Kombinationen aus zumindest zwei von in der Beschreibung, den Ansprüchen und/oder den Figuren offenbarten Merkmalen.This object is achieved with regard to the protective layer arrangement having the feature of claim 1 and with regard to the component having the features of claim 9. In front- Partial developments of the invention are specified in the dependent claims. All combinations of at least two features disclosed in the description, the claims and / or the figures fall within the scope of the invention.
Der Erfindung liegt der Gedanke zugrunde, zusätzlich zu einer ersten Haftvermittlerschicht aus reinem Chrom oder zumindest mit einem Chromanteil eine zweite Haftvermittler- schicht vorzusehen, die einen Kohlenstoffanteil enthält. Durch diese Maßnahme kann die Haftfestigkeit der Verschleißschutzschichtanordnung auf einem zu beschichtenden Bauteil, insbesondere für ein Kraftstoff-Einspritzsystem, wesentlich verbessert werden. Bevorzugt ist die Schutz- schicht mit tetragonal gebundenem, amorphem Kohlenstoff Wasserstofffrei . Insbesondere kann eine verbesserte Temperaturbeständigkeit bei Prüftests unter einer inerten Gasatmosphäre bei einer Temperatur von etwa 4000C über einen Zeitraum von 150 Stunden erreicht werden.The invention is based on the idea, in addition to a first adhesion promoter layer of pure chromium or at least with a chromium portion, to provide a second adhesion promoter layer which contains a carbon content. By virtue of this measure, the adhesive strength of the wear protection layer arrangement on a component to be coated, in particular for a fuel injection system, can be substantially improved. The protective layer with tetragonal bonded, amorphous carbon is preferably hydrogen-free. In particular, an improved temperature resistance in test tests under an inert gas atmosphere at a temperature of about 400 0 C over a period of 150 hours can be achieved.
In Weiterbildung der Erfindung ist mit Vorteil vorgesehen, dass die zweite Haftvermittlerschicht zusätzlich zu dem Kohlenstoffanteil einen Chromanteil aufweist. Anders ausgedrückt ist die zweite Haftvermittlerschicht bevorzugt als Mischschicht, umfassend Kohlenstoffanteile und Chromanteile, ausgeführt. Durch diese Maßnahme wird eine besonders haftfeste Schutzschichtanordnung erhalten.In a development of the invention, it is advantageously provided that the second adhesion promoter layer has a chromium content in addition to the carbon content. In other words, the second adhesion promoter layer is preferably designed as a mixed layer comprising carbon components and chromium components. By this measure, a particularly adherent protective layer arrangement is obtained.
Von besonderem Vorteil ist eine Ausführungsform, bei der die zweite Haftvermittlerschicht als sogenannte Gradientenschicht mit an mindestens zwei Stellen unterschiedlichem Chrom-/KohlenstoffVerhältnis ausgebildet ist. Zur weiteren Verbesserung der Haftfestigkeit der Verschleißschutz- Schichtanordnung ist es dabei bevorzugt, wenn der Kohlenstoffanteil mit zunehmender Schichtdicke in Richtung Schutzschicht, bevorzugt linear, zunimmt.Of particular advantage is an embodiment in which the second adhesion promoter layer is formed as a so-called gradient layer with at least two locations different chromium / carbon ratio. To further improve the adhesive strength of the wear protection Layer arrangement, it is preferred if the carbon content increases with increasing layer thickness in the direction of the protective layer, preferably linear.
Von ganz besonderem Vorteil ist eine Ausführungsform der Verschleißschutzschichtanordnung, bei der die Schutzschicht aus tetragonal gebundenem, amorphem Kohlenstoff unmittelbar auf die zweite Haftvermittlerschicht aufgebracht ist. Besonders bevorzugt bildet die Schutzschicht dabei eine äuße- re Schicht der Verschleißschutzschichtanordnung, also eine Deckschicht, die in unmittelbarem Kontakt mit Betriebsmedien, beispielsweise Kraftstoff, gelangt.Of very particular advantage is an embodiment of the wear protection layer arrangement in which the protective layer of tetragonal bonded amorphous carbon is applied directly to the second adhesion promoter layer. In this case, the protective layer particularly preferably forms an outer layer of the wear protection layer arrangement, that is to say a cover layer which comes into direct contact with operating media, for example fuel.
Gute Ergebnisse im Hinblick auf eine optimierte Haftfestig- keit der Verschleißschutzschichtanordnung werden erreicht, wenn die erste Haftvermittlerschicht und/oder die zweite Haftvermittlerschicht eine Schichtdicke aus einem Wertebereich zwischen etwa 50nm und etwa 300nm aufweisen/aufweist. Besonders bevorzugt ist die Gesamtdicke der Verschleiß- Schichtanordnung aus einem Wertebereich zwischen etwa lμm und lOμm gewählt.Good results with regard to an optimized adhesive strength of the wear protection layer arrangement are achieved if the first adhesion promoter layer and / or the second adhesion promoter layer have / has a layer thickness of a value range between approximately 50 nm and approximately 300 nm. Particularly preferably, the total thickness of the wear layer arrangement is selected from a value range between about 1 μm and 10 μm.
Besonders bevorzugt ist es, die erste Haftvermittlerschicht mittels eines PVD-Verfahrens (physikalische Gasphasenab- Scheidung) unmittelbar auf die Oberfläche des zu beschichtenden, vorzugsweise zumindest im zu beschichtenden Bereich aus Stahl bestehenden, ersten Bauteils aufzubringen. Mit Vorteil wird hierzu ein Chrom-Target gesputtert, in dem dieses mit inerten Argonionen beschossen wird. Idealerweise wird auch die Schutzschicht mittels eines PVD-Verfahrens, vorzugsweise unter Vakuum, ganz bevorzugt durch Lichtbogenverdampfen (Arc-PVD) aufgebracht. Für den Fall, dass die zweite Haftvermittlerschicht als Mischschicht umfassend o- der bestehend aus Chrom und Kohlenstoff ausgebildet wird, ist es bevorzugt, diese zweite Haftvermittlerschicht durch ein kombiniertes PVD/CVD-Verfahren (CVD = chemische Gaspha- senabscheidung) aufzubringen, wobei das Chrom-Target wei- terhin durch Ionenbeschuß zerstäubt und damit in die Gasphase überführt wird und zusätzlich Acetylengas (Ethin) eingeleitet wird, was zur Aufkonzentration von Kohlenstoff in der zweiten Haftvermittlerschicht führt. Durch eine geeignete Prozessführung kann der Anteil an Kohlenstoff mit zunehmender Schichtdicke erhöht werden.It is particularly preferred to apply the first adhesion promoter layer by means of a PVD process (physical vapor deposition) directly onto the surface of the first component to be coated, preferably at least in the region of steel to be coated. Advantageously, this is sputtered a chromium target, in which this is bombarded with inert argon ions. Ideally, the protective layer is applied by means of a PVD process, preferably under vacuum, most preferably by arc vapor deposition (Arc-PVD). In the event that the second adhesion promoter layer as a mixed layer comprising o- is formed consisting of chromium and carbon, it is preferred to apply this second adhesion promoter layer by a combined PVD / CVD (CVD = chemical vapor deposition), wherein the chromium target further atomized by ion bombardment and thus in the gas phase In addition, acetylene gas (ethyne) is introduced, resulting in the concentration of carbon in the second adhesion promoter layer. By suitable process control, the proportion of carbon can be increased with increasing layer thickness.
Die Erfindung führt auch auf ein Bauelement, insbesondere eines Kraftstoff-Einspritzsystems. Ganz besonders bevorzugt besteht das Bauelement, zumindest in dem zu beschichtenden Bereich, aus Stahl. Das Bauelement zeichnet sich durch eine nach dem Konzept der Erfindung ausgebildete, zuvor beschriebene Verschleißschutzschichtanordnung aus. Ganz besonders bevorzugt handelt es sich bei dem Bauelement um ein Bestandteil eines Kraftstoffinjektors, insbesondere um eine Düsennadel, die vorzugsweise zumindest im Sitzbereich mit einer Verschleißschutzschichtanordnung versehen ist. Ebenso kann es sich bei dem Bauelement um ein Bestandteil einer Kraftstoff-Hochdruckpumpe, vorzugsweise um einen starken Beanspruchungen ausgesetzten Pumpenflügel, handeln.The invention also leads to a component, in particular a fuel injection system. Most preferably, the device, at least in the area to be coated, made of steel. The device is characterized by a trained according to the concept of the invention, previously described wear protection layer arrangement. The component is very particularly preferably a component of a fuel injector, in particular a nozzle needle, which is preferably provided with a wear protection layer arrangement at least in the seating area. Likewise, the component may be a component of a high-pressure fuel pump, preferably a pump blade exposed to heavy loads.
Kurze Beschreibung der ZeichnungenBrief description of the drawings
Weitere Vorteile, Merkmale und Einzelheiten der Erfindung ergeben sich aus der nachfolgenden Beschreibung eines be- vorzugten Ausführungsbeispiels sowie anhand der Zeichnung. Diese zeigt in der einzigen Fig. 1 ein mit einer dreischichtigen Verschleißschutzschichtanordnung beschichtetes Bauelement aus Stahl eines Kraftstoff-Einspritzsystems.Further advantages, features and details of the invention will become apparent from the following description of a preferred embodiment and with reference to the drawing. This shows in the only one Fig. 1 is a coated with a three-layer wear protection layer assembly of steel component of a fuel injection system.
Ausführungsform der ErfindungEmbodiment of the invention
In Fig. 1 ist ein mit einer Verschleißschutzschichtanordnung 1 beschichtetes Bauelement B aus Stahl gezeigt. Bei dem Bauelement B handelt es sich um ein Bauelement eines Einspritzsystems, vorzugsweise um eine Düsennadelspitze eines Kraftstoff-Inj ektors oder einen Pumpenflügel, einer Kraftstoff-Hochdruckpumpe zur Versorgung eines Kraftstoff- Hochdruckspeichers (Rail) .In Fig. 1, a coated with a wear protection layer assembly 1 component B made of steel is shown. The component B is a component of an injection system, preferably a nozzle needle tip of a fuel injector or a pump impeller, of a high-pressure fuel pump for supplying a high-pressure fuel accumulator (rail).
Wie sich aus Fig. 1 ergibt, ist die Verschleißschutzschichtanordnung 1 unmittelbar auf eine äußere Oberfläche O des Bauelementes B aufgebracht. Die Verschleißschutzschichtanordnung 1 umfasst eine erste HaftvermittlerschichtAs is apparent from Fig. 1, the wear protection layer assembly 1 is applied directly to an outer surface O of the component B. The wear protection layer arrangement 1 comprises a first adhesion promoter layer
2 aus reinem Chrom. Die Schichtdicke dieser ersten Haftver- mittlerschicht 2 ist aus einem Wertebereich zwischen etwa2 of pure chrome. The layer thickness of this first adhesion promoter layer 2 is from a value range between approximately
50nm und etwa 300nm gewählt. Die erste Haftvermittlerschicht 2 ist mittels eines PVD-Verfahrens, umfassend das Beschießen eines Chrom-Targets mit Argonionen auf die Oberfläche O aufgebracht.50nm and about 300nm chosen. The first adhesion promoter layer 2 is applied to the surface O by means of a PVD process comprising bombarding a chromium target with argon ions.
Unmittelbar an die erste Haftvermittlerschicht 2 grenzt eine zweite Haftvermittlerschicht 3 an. Diese ist als Mischschicht, umfassend die Bestandteile Chrom und Kohlenstoff, ausgebildet. Dabei nimmt der Kohlenstoffanteil der als Gra- dientenschicht ausgebildeten zweiten HaftvermittlerschichtImmediately adjoining the first adhesion promoter layer 2 is a second adhesion promoter layer 3. This is formed as a mixed layer comprising the components chromium and carbon. In this case, the carbon content of the second adhesion promoter layer formed as a gradient layer increases
3 ausgehend von der ersten Haftvermittlerschicht 2 in Richtung in der Zeichnungsebene nach oben, also mit zunehmender Schichtdicke zu. Die zweite Haftvermittlerschicht 3 weist ebenfalls eine Schichtdicke aus einem Wertebereich zwischen etwa 50nm und etwa 300nm auf. Zum Aufbringen der zweiten Haftvermittlerschicht 3 wird ein kombiniertes PVD/CVD- Verfahren angewendet, wobei zu den Argonionen zum Sputtern eines Chrom-Targets Acetylengas zugeleitet wird.3 starting from the first bonding agent layer 2 in the direction of the drawing plane upwards, ie with increasing layer thickness. The second adhesive layer 3 has likewise a layer thickness from a value range between about 50 nm and about 300 nm. For applying the second adhesion promoter layer 3, a combined PVD / CVD method is used, wherein acetylene gas is fed to the argon ions for sputtering a chromium target.
Unmittelbar auf der zweiten Haftvermittlerschicht 3 befindet sich die als Deckschicht dienende Schutzschicht 4. Diese besteht aus tetragonal gebundenem, amorphen, wasser- stofffreien Kohlenstoff. Die Schutzschicht 4 wird mittels eines PVD-Verfahrens, bei dem Kohlenstoff mittels eines Va- kuum-Lichbogens verdampft, auf die zweite Haftvermittlerschicht 3 aufgebracht.Directly on the second adhesion promoter layer 3 is the protective layer 4 serving as a cover layer. This consists of tetragonal bonded, amorphous, hydrogen-free carbon. The protective layer 4 is applied to the second adhesion promoter layer 3 by means of a PVD process in which carbon evaporates by means of a vacuum arc.
Die in Fig. 1 gezeigte, auf das Bauelement B aufgebrachte Verschleißschutzschichtanordnung 1 weist eine besonders gute Haftfestigkeit und Temperaturbeständigkeit auf. Insbesondere ist die Verschleißschutzschichtanordnung 1 temperaturbeständig bei einem Prüfverfahren, bei dem das beschich- tete Bauelement B unter inerter Gasatmosphäre für 150 Stunden mit einer Temperatur von etwa 4000C beaufschlagt wird. The anti-wear layer arrangement 1 shown in FIG. 1 and applied to the component B has a particularly good adhesive strength and temperature resistance. In particular, the wear protection layer arrangement 1 is temperature-resistant in a test method in which the coated component B is exposed to an inert gas atmosphere for 150 hours at a temperature of about 400 0 C.

Claims

Ansprüche claims
1. Verschleißschutzschichtanordnung, insbesondere für hohen Drücken und Temperaturen ausgesetzten Bauelemente (B) eines Kraftstoffeinspritzsystems, mit einer aus tetragonal gebundenem amorphen Kohlenstoff gebildeten oder einen Anteil an tetragonal gebundenem amorphen Kohlenstoff aufweisenden Schutzschicht (4), und mit einer aus Chrom gebildeten oder einen Chrom-Anteil aufweisenden ersten Haftvermittlerschicht (2),1. Wear protection layer arrangement, in particular for components exposed to high pressures and temperatures (B) of a fuel injection system, having a protective layer (4) formed from tetragonal bonded amorphous carbon or containing a proportion of tetragonal bonded amorphous carbon, and having a chromium-forming or chromium-containing Share having first adhesive layer (2),
gekennzeichnet durch,marked by,
mindestens eine an die erste Haftvermittlerschicht (2) angrenzende, einen Kohlenstoff-Anteil aufweisende zweite Haftvermittlerschicht (3) .at least one second adhesion promoter layer (3), which has a carbon content and is adjacent to the first adhesion promoter layer (2).
2. Verschleißschutzschichtanordnung nach Anspruch 1, dadurch gekennzeichnet, dass die zweite Haftvermittlerschicht (3) einen Anteil Chrom aufweist.2. Wear protection layer arrangement according to claim 1, characterized in that the second adhesion promoter layer (3) has a proportion of chromium.
3. Verschleißschutzschichtanordnung nach Anspruch 2, dadurch gekennzeichnet, dass die zweite Haftvermittlerschicht (3) als Gradientenschicht mit unterschiedlichen Chrom/Kohlenstoffgradienten ausgebildet ist.3. Wear protection layer arrangement according to claim 2, characterized in that the second adhesion promoter layer (3) is designed as a gradient layer with different chromium / carbon gradients.
4. Verschleißschutzschichtanordnung nach einem der An- sprüche 2 oder 3, dadurch gekennzeichnet, dass der Kohlenstoff-Anteil in der zweiten Haftvermittlerschicht (3) ausgehend von der ersten Haftver- mittlerschicht (2) mit zunehmender Schichtdicke zunimmt .4. wear protection layer arrangement according to one of claims 2 or 3, characterized in that the carbon content in the second adhesion promoter layer (3) starting from the first adhesion middle layer (2) increases with increasing layer thickness.
5. Verschleißschutzschichtanordnung nach einem der vor- hergehenden Ansprüche, dadurch gekennzeichnet, dass die Schutzschicht (4) unmittelbar auf die zweite Haftvermittlerschicht (3) aufgebracht ist.5. Wear protection layer arrangement according to one of the preceding claims, characterized in that the protective layer (4) is applied directly to the second adhesion promoter layer (3).
6. Verschleißschutzschichtanordnung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die erste Haftvermittlerschicht (2) und/oder die zweite Haftvermittlerschicht (3) eine Schichtdicke aus einem Wertebereich zwischen etwa 50nm und 300nm aufweisen/aufweist .6. Wear protection layer arrangement according to one of the preceding claims, characterized in that the first adhesion promoter layer (2) and / or the second adhesion promoter layer (3) has a layer thickness of a value range between about 50nm and 300nm / has.
7. Verschleißschutzschichtanordnung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Gesamtdicke der Verschleißschutzschichtanordnung (1) aus einem Wertebereich zwischen etwa lμm und etwa lOμm gewählt ist.7. Wear protection layer arrangement according to one of the preceding claims, characterized in that the total thickness of the wear protection layer arrangement (1) is selected from a value range between about lμm and about lOμm.
8. Verschleißschutzschichtanordnung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die erste Haftvermittlerschicht (2) und/oder die Schutzschicht (4) mittels PVD aufgebracht sind/ist und/oder dass die zweite Haftvermittlerschicht (3) durch ein kombiniertes PVD/CVD-Verfahren aufgebracht ist. 8. Wear protection layer arrangement according to one of the preceding claims, characterized in that the first adhesion promoter layer (2) and / or the protective layer (4) are applied by means of PVD / and / or that the second adhesion promoter layer (3) by a combined PVD / CVD Method is applied.
9. Bauelement, insbesondere eines Kraftstoffeinspritzsys- tems, vorzugsweise aus Stahl, mit einer Verschleißschutzschichtanordnung (1) nach einem der vorhergehenden Ansprüche.9. Component, in particular a Kraftstoffeinspritzsys- system, preferably made of steel, with a wear protection layer assembly (1) according to one of the preceding claims.
10. Bauelement nach Anspruch 9, dadurch gekennzeichnet, dass das Bauelement (B) ein Bestandteil eines Kraftstoff-Injektors, insbesondere eine Düsennadel, oder ein Bestandteil einer Kraftstoff-Hochdruckpumpe, insbesondere ein Pumpenflügel, ist. 10. The component according to claim 9, characterized in that the component (B) is a component of a fuel injector, in particular a nozzle needle, or a component of a high-pressure fuel pump, in particular a pump blade.
PCT/EP2009/059696 2008-07-28 2009-07-28 Anti-wear layer system and component comprising an anti-wear layer arrangement WO2010012701A1 (en)

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