WO2016198205A1 - Method for coating a valve of an internal combustion engine - Google Patents

Method for coating a valve of an internal combustion engine Download PDF

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Publication number
WO2016198205A1
WO2016198205A1 PCT/EP2016/059295 EP2016059295W WO2016198205A1 WO 2016198205 A1 WO2016198205 A1 WO 2016198205A1 EP 2016059295 W EP2016059295 W EP 2016059295W WO 2016198205 A1 WO2016198205 A1 WO 2016198205A1
Authority
WO
WIPO (PCT)
Prior art keywords
valve
nickel
bath
coated
boron carbide
Prior art date
Application number
PCT/EP2016/059295
Other languages
German (de)
French (fr)
Inventor
Andreas Dogar
Stephan Körner
Reinhard Rose
Original Assignee
Mahle International 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 Mahle International Gmbh filed Critical Mahle International Gmbh
Priority to EP16718679.0A priority Critical patent/EP3307926A1/en
Publication of WO2016198205A1 publication Critical patent/WO2016198205A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
    • F01L3/04—Coated valve members or valve-seats
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2301/00—Using particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2301/00—Using particular materials
    • F01L2301/02—Using ceramic materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2303/00—Manufacturing of components used in valve arrangements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2820/00—Details on specific features characterising valve gear arrangements
    • F01L2820/01—Absolute values

Definitions

  • the present invention relates to a method for coating a valve of an internal combustion engine, in particular at least one location of a valve stem of the valve.
  • the invention also relates to a valve coated with such a method of an internal combustion engine and an internal combustion engine with at least one such valve.
  • valves in an internal combustion engine or their valve shafts are nowadays coated with a chromium-containing wear protection layer, since the valves are exposed to a large tribological load, in particular in the region of the valve stem and here in the region of a valve guide, and the wear protection layer ensures friction and wear-resistant operation should.
  • Chromium (VI) that is, chromium trioxide plays a vital economic role in all types of chromium plating, that is both chrome plating of plastics and iron or non-ferrous metals, but is subject to both strict regulations and special supervision due to its contentious nature even in a ban, at least for certain applications.
  • the present invention therefore deals with the problem of specifying a method by means of which an extremely resistant and load-bearing wear protection layer, in particular on a position of a valve stem of a valve of an internal combustion engine can be applied without this chromium would be required.
  • This problem is solved according to the invention by the subject matter of independent claim 1.
  • Advantageous embodiments are the subject of the dependent claims.
  • the present invention is based on the general idea to provide an alternative method for coating a valve of an internal combustion engine, in particular at least one point of a valve stem of the valve, in which a durable and at the same time durable wear protection layer can be applied, which no longer has chromium.
  • the valve is first immersed in the inventive method, at least with the point to be coated in a nickel (Ni) pure bath as a primer, in particular made of steel or stainless steel valves without such a primer or such an adhesive layer would not be permanently coated.
  • the valve is at least with the point to be coated in a nickel (Ni) and boron carbide (BC) exhibiting bath or in a nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (BC) exhibiting bath dipped.
  • This dispersion layer is the functional layer and serves as wear protection as an alternative coating for chromium coating.
  • Boron carbide as a particle is a very hard material with a Mohs hardness of 9.3, which can be used as a wear-resistant material.
  • Boron carbide is a non-oxide ceramic, which is characterized by particular hardness and toughness similar to silicon carbide or silicon nitride.
  • Boron carbide ceramic is also extremely resistant to wear, even at low temperatures. In terms of hardness, it is even more resistant to wear at low temperatures than silicon nitride ceramics. Also in terms of chemical resistance, boron carbide has a very high resistance, which is particularly in the field of relatively aggressive media, such as oils, a great advantage.
  • a bath containing nickel (Ni) and boron carbide (BC) is used, with a boron carbide content of 30 g / l to 65 g / l, in particular with a boron carbide content of 50 g / l.
  • a wear protection layer can be achieved in which the wear occurring during operation of the internal combustion engine is virtually zero and the material transfer at one tenth of the material transfer compared to one of chromium trained wear protection layer is located.
  • the wear ie the material removal of the wear protection layer itself
  • the so-called transfer of material ie the transfer of coating material into the valve guide. Both can be achieved with the previously described and nickel (Ni) and boron carbide (BC) having wear protection layer.
  • the valve is immersed, at least with the point to be coated, in a bath comprising nickel (Ni), boron carbide (B C) and hexagonal boron nitride (h (BN)).
  • a bath comprising nickel (Ni), boron carbide (B C) and hexagonal boron nitride (h (BN)).
  • the content of boron nitride (h (BN)) should be between 10 g / l and 25 g / l, in particular between 18 and 22 g / l, particularly preferably about 20 g / l.
  • a boron nitride content of about 20 g / l in the nickel electrolyte wear can be achieved, which in turn is almost zero.
  • substantial advantages in terms of friction can be achieved.
  • the valve is polished and / or ground at least at the point to be coated.
  • valve is coated with the method according to the invention at least at one point of the valve stem, that is, the wear protection layer according to the invention is applied, it being understood that this wear protection layer is also applied to the entire valve or to other locations, for example can be applied to a valve seat ring.
  • the present invention is further based on the general idea to provide a valve of an internal combustion engine, which has been coated at least one point by the method described above.
  • the valve according to the invention has a nickel (Ni) adhesive layer and an overlying wear protection layer of nickel (Ni) and boron carbide (B C).
  • the wear protection layer is reworked, for example, polished or ground.
  • the wear protection layer has a layer thickness d between 5 ⁇ m and 15 ⁇ m.
  • a thin wear protection layer allows the wear resistance of the valve over its entire life, being used as a primer or adhesive layer for the wear protection layer, the underlying nickel layer, which allows reliable adhesion of the wear protection layer on stainless steel surfaces.
  • This nickel interlayer which is applied in a nickel chloride electrolyte is imperative, especially when using high-alloy Stainless steels such as X50. Otherwise, sufficient adhesion of the nickel dispersion layer can not be achieved.
  • the sole FIGURE 1 shows a valve according to the invention with a wear protection layer applied thereto according to the invention.
  • a valve 1 according to the invention of an internal combustion engine 2 which is not further illustrated, has a valve disk 3 and a valve stem 5 connected thereto via a valve throat 4. At least at one point in the region of the valve stem 5, on which it is guided in a valve guide 6, the valve 1 according to the invention is provided with a wear protection layer 7.
  • the valve guide 6 may be formed of a sintered material. Due to the very good wettability of the nickel dispersion layer with oil, the wear of the valve guide is significantly reduced compared to a chrome-coated valve stem.
  • the BC boron carbide
  • the BC boron carbide
  • the BC can transform at high temperatures (380-420) ° C and in the presence of oxygen a graphite-like structure (boron oxide).
  • the wear protection layer 7 now comprises nickel (Ni) and boron carbide (BC), as a result of which it has both high chemical resistance and high wear resistance.
  • a surface of the wear-resistant layer 7 is reworked, in particular polished and / or ground.
  • valve 1 according to the invention or the coating applied thereto is produced as follows:
  • the valve 1 is dipped at least with the point to be coated, in particular in the region of the valve stem 5, in a nickel (Ni) -containing pure bath as a primer, whereby the adhesive layer 8 is applied to the surface of the valve stem 5.
  • This adhesive layer 8 is required for long-lasting and reliable connection of the wear protection layer 7 with the valve 1.
  • the valve 1 is immersed at least with the point to be coated in a bath having nickel (Ni) and boron carbide (BC) or in a nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (BC) , whereby the actual wear protection layer 7 is applied.
  • the valve 1 is subsequently reworked at least in the region of the wear protection layer 7, for example polished and / or ground.
  • the bath used to produce the wear protection layer 7 has a boron carbide content of 30 g / l to 65 g / l, in particular a boron carbide content of about 50 g / l, which has been found to result in almost zero wear and in Representative tests a material transfer is only 1/10 of the material transfer compared to the use of a chromium-containing wear protection layer.
  • wear resistance in particular two characteristic values are of particular importance, on the one hand the wear, ie the material removal of the wear protection layer 7 itself and, secondly, the so-called material transfer, ie the transfer of coating material into the valve guide 6.
  • a bath containing nickel (Ni) and boron carbide (B C) can also be used to produce the wear protection layer 7, this bath additionally having hexagonal boron nitride (h (BN)).
  • the boron nitride content (h (BN)) of this bath is between 10 g / l and 25 g / l, in particular between 18 and 22 g / l, particularly preferably about 20 g / l.
  • the latter concentration or the last-mentioned boron nitride content of about 20 g / l has proved to be particularly advantageous with respect to the material transfer.
  • the bath may additionally contain hard material particles. At least one of these hard material particles has or consists of silicon carbide (SiC), tungsten carbide (WC), titanium nitride (TiN), silicon nitride (Si 3 N), cubic boron nitride (c-BN) or aluminum oxide (Al 2 O 3).
  • the hard material particles usually have a diameter which is on average less than or equal to 0.1 ⁇ to 3 ⁇ , in particular from 0.8 ⁇ to 2.5 ⁇ .
  • the wear protection layer 7 itself has a layer thickness d, which has between 5 and 15 ⁇ .
  • the wear protection layer 7 With the wear protection layer 7 according to the invention, it is therefore possible to replace a wear protection layer previously used in this area and containing chromium, which has considerable advantages with regard to the safety in terms of the environment and health and with the customer requirements changed as a result. brings. In addition, with such and now no longer chromium-containing wear protection layer 7 and the concerns regarding the use of chrome accounted for. Of particular importance is that the wear protection layer 7 of the invention has an extremely high wear resistance and high chemical resistance and also has a material transfer, which is only 1/10 of the material transfer of previous chromium-containing wear protection layers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Lift Valve (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)

Abstract

The invention relates to a method for coating a valve (1) of an internal combustion engine (2), in particular a place on a valve stem (5) of the valve (1), in which - the valve (1) is immersed, at least at the place that is to be coated, in a bath of just nickel (Ni) as a bonding agent, - the valve (1) is immersed, at least with the place that is to be coated, in a bath comprising nickel (Ni) and boron carbide (B4C) or in a bath comprising nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (B4C), - the valve (1) is reworked, at least at the place that is to be coated. This particularly allows a previously chromium-containing wear-resistant layer to be replaced.

Description

Verfahren zum Beschichten eines Ventils einer Brennkraftmaschine  Process for coating a valve of an internal combustion engine
Die vorliegende Erfindung betrifft ein Verfahren zum Beschichten eines Ventils einer Brennkraftmaschine, insbesondere zumindest einer Stelle eines Ventilschaftes des Ventils. Die Erfindung betrifft außerdem ein mit einem derartigen Verfahren beschichtetes Ventil einer Brennkraftmaschine sowie eine Brennkraftmaschine mit zumindest einem solchen Ventil. The present invention relates to a method for coating a valve of an internal combustion engine, in particular at least one location of a valve stem of the valve. The invention also relates to a valve coated with such a method of an internal combustion engine and an internal combustion engine with at least one such valve.
Üblicherweise werden Ventile in einer Brennkraftmaschine bzw. deren Ventilschäfte heutzutage mit einer chromhaltigen Verschleißschutzschicht beschichtet, da die Ventile insbesondere im Bereich des Ventilschaftes und hier im Bereich einer Ventilführung einer großen tribologischen Belastung ausgesetzt sind und mit der Verschleißschutzschicht ein reibungs- und zugleich verschleißarmer Betrieb sichergestellt werden soll. Normally, valves in an internal combustion engine or their valve shafts are nowadays coated with a chromium-containing wear protection layer, since the valves are exposed to a large tribological load, in particular in the region of the valve stem and here in the region of a valve guide, and the wear protection layer ensures friction and wear-resistant operation should.
Chrom (VI) das heißt Chromtrioxid spielt bei Verchromungen jeglicher Art, das heißt sowohl bei einer Verchromung von Kunststoffen als auch von Eisen oder Nichteisenmetallen eines wesentliche wirtschaftliche Rolle, unterliegt jedoch aufgrund seiner umstrittenen Eigenschaften sowohl strengen Regulierungen als auch einer besonderen Aufsicht, die unter Umständen sogar in ein Verbot zumindest für bestimmte Anwendungen münden dürfte. Chromium (VI) that is, chromium trioxide plays a vital economic role in all types of chromium plating, that is both chrome plating of plastics and iron or non-ferrous metals, but is subject to both strict regulations and special supervision due to its contentious nature even in a ban, at least for certain applications.
Die vorliegende Erfindung beschäftigt sich daher mit dem Problem, ein Verfahren anzugeben, mittels welchem eine extrem beständige und belastbare Verschleißschutzschicht, insbesondere auf eine Stelle eines Ventilschaftes eines Ventils einer Brennkraftmaschine aufgebracht werden kann, ohne dass hierfür Chrom erforderlich wäre. Dieses Problem wird erfindungsgemäß durch den Gegenstand des unabhängigen Anspruchs 1 gelöst. Vorteilhafte Ausführungsformen sind Gegenstand der abhängigen Ansprüche. The present invention therefore deals with the problem of specifying a method by means of which an extremely resistant and load-bearing wear protection layer, in particular on a position of a valve stem of a valve of an internal combustion engine can be applied without this chromium would be required. This problem is solved according to the invention by the subject matter of independent claim 1. Advantageous embodiments are the subject of the dependent claims.
Die vorliegende Erfindung beruht auf dem allgemeinen Gedanken, ein alternatives Verfahren zum Beschichten eines Ventils einer Brennkraftmaschine, insbesondere zumindest einer Stelle eines Ventilschafts des Ventils anzugeben, bei welchem eine beständige und zugleich belastbare Verschleißschutzschicht aufgebracht werden kann, die kein Chrom mehr aufweist. Hierzu wird das Ventil bei dem erfindungsgemäßen Verfahren zunächst zumindest mit der zu beschichtenden Stelle in ein Nickel (Ni) Reinbad als Haftvermittler getaucht, wobei insbesondere aus Stahl oder Edelstahl hergestellte Ventile ohne einen derartigen Haftvermittler bzw. eine derartige Haftschicht, nicht dauerhaft zu beschichten wären. Anschließend wird das Ventil zumindest mit der zu beschichtenden Stelle in ein Nickel (Ni) und Borcarbid (B C) aufweisendes Bad oder in ein Nickel-Wolfram (Ni-W) oder Nickel-Eisen (Ni-Fe) und Borcarbid (B C) aufweisendes Bad getaucht. Diese Dispersionsschicht ist die Funktionsschicht und dient als Verschleißschutz als alternative Beschichtung zur Chrombeschichtung. Borcarbid als Partikel ist ein sehr hartes Material mit einer Mohshärte von 9,3, welches als verschleißbeständiges Material genutzt werden kann. Borcarbid ist dabei eine Nichtoxid-Keramik, die sich ähnlich wie Siliziumcarbid oder Siliziumnitrid durch besondere Härte und Zähigkeit auszeichnet. Borcarbid-Keramik ist darüber hinaus äußerst verschleißbeständig auch bei niedrigen Temperaturen. In ihrer Härte ist sie bei niedrigen Temperaturen sogar verschleißbeständiger als Siliziumnitrid- Keramiken. Auch hinsichtlich der chemischen Beständigkeit weist Borcarbid eine sehr hohe Beständigkeit auf, was insbesondere im Bereich der vergleichsweise aggressiven Medien, wie beispielsweise Ölen, von großem Vorteil ist. Bei einer vorteilhaften Weiterbildung der erfindungsgemäßen Lösung wird ein Nickel (Ni) und Borcarbid (B C) aufweisendes Bad verwendet, mit einem Borcar- bidgehalt von 30 g/l bis 65 g/l, insbesondere mit einem Borcarbidgehalt von 50 g/l. Hierbei hat sich gezeigt, dass insbesondere bei einer Dosierung des Borcar- bidgehalts von 50 g/l eine Verschleißschutzschicht erreicht werden kann, bei welcher der im Betrieb der Brennkraftmaschine auftretende Verschleiß nahezu Null und der Materialübertrag bei einem Zehntel des Materialübertrags im Vergleich zu einer aus Chrom ausgebildeten Verschleißschutzschicht liegt. Zur Beurteilung der Verschleißbeständigkeit sind dabei zwei Kennwerte von besonderem Interesse, zum einen der Verschleiß, also der Materialabtrag der Verschleißschutzschicht selbst und zum anderen der sogenannte Materialübertrag, also der Transfer von Beschichtungsmaterial in die Ventilführung. Beides kann mit der zuvor beschriebenen und Nickel (Ni) und Borcarbid (B C) aufweisenden Verschleißschutzschicht erreicht werden. The present invention is based on the general idea to provide an alternative method for coating a valve of an internal combustion engine, in particular at least one point of a valve stem of the valve, in which a durable and at the same time durable wear protection layer can be applied, which no longer has chromium. For this purpose, the valve is first immersed in the inventive method, at least with the point to be coated in a nickel (Ni) pure bath as a primer, in particular made of steel or stainless steel valves without such a primer or such an adhesive layer would not be permanently coated. Subsequently, the valve is at least with the point to be coated in a nickel (Ni) and boron carbide (BC) exhibiting bath or in a nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (BC) exhibiting bath dipped. This dispersion layer is the functional layer and serves as wear protection as an alternative coating for chromium coating. Boron carbide as a particle is a very hard material with a Mohs hardness of 9.3, which can be used as a wear-resistant material. Boron carbide is a non-oxide ceramic, which is characterized by particular hardness and toughness similar to silicon carbide or silicon nitride. Boron carbide ceramic is also extremely resistant to wear, even at low temperatures. In terms of hardness, it is even more resistant to wear at low temperatures than silicon nitride ceramics. Also in terms of chemical resistance, boron carbide has a very high resistance, which is particularly in the field of relatively aggressive media, such as oils, a great advantage. In an advantageous development of the solution according to the invention, a bath containing nickel (Ni) and boron carbide (BC) is used, with a boron carbide content of 30 g / l to 65 g / l, in particular with a boron carbide content of 50 g / l. It has been found that, in particular when the boron carbide content of 50 g / l is metered, a wear protection layer can be achieved in which the wear occurring during operation of the internal combustion engine is virtually zero and the material transfer at one tenth of the material transfer compared to one of chromium trained wear protection layer is located. To assess the wear resistance, two parameters are of particular interest, on the one hand the wear, ie the material removal of the wear protection layer itself and, on the other hand, the so-called transfer of material, ie the transfer of coating material into the valve guide. Both can be achieved with the previously described and nickel (Ni) and boron carbide (BC) having wear protection layer.
Bei einer weiteren vorteilhaften Ausführungsform der erfindungsgemäßen Lösung wird das Ventil zumindest mit der zu beschichtenden Stelle in eine Nickel (Ni), Borcarbid (B C) und hexagonalem Bornitrid (h(BN)) aufweisendes Bad getaucht. Hierbei sollte der Gehalt an Bornitrid (h(BN)) zwischen 10 g/l und 25 g/l, insbesondere zwischen 18 und 22 g/l, besonders bevorzugt bei ca. 20 g/l liegen. Insbesondere bei einem Bornitridgehalt von ca. 20 g/l im Nickelelektrolyten kann ein Verschleiß erreicht werden, der wiederum nahezu bei Null liegt. Bei einer derartigen Nickeldispersionsschicht können darüber hinaus wesentliche Vorteile hinsichtlich der Reibung erzielt werden. In a further advantageous embodiment of the solution according to the invention, the valve is immersed, at least with the point to be coated, in a bath comprising nickel (Ni), boron carbide (B C) and hexagonal boron nitride (h (BN)). In this case, the content of boron nitride (h (BN)) should be between 10 g / l and 25 g / l, in particular between 18 and 22 g / l, particularly preferably about 20 g / l. In particular, with a boron nitride content of about 20 g / l in the nickel electrolyte wear can be achieved, which in turn is almost zero. In addition, with such a nickel dispersion layer, substantial advantages in terms of friction can be achieved.
Bei einer vorteilhaften Weiterbildung der erfindungsgemäßen Lösung wird das Ventil zumindest an der zu beschichtenden Stelle poliert und/oder geschliffen. Beide, lediglich rein exemplarisch an dieser Stelle aufgezählten Nachbearbei- tungsverfahren, erhöhen die Oberflächengüte der Verschleißschutzschicht und tragen damit zur Verbesserung der Verschleißeigenschaften bei. In an advantageous development of the solution according to the invention, the valve is polished and / or ground at least at the point to be coated. Both post-processing examples, which are given purely by way of example at this point, tion method, increase the surface quality of the wear protection layer and thus contribute to the improvement of the wear properties.
In den vorherigen Absätzen wurde dabei stets erwähnt, dass das Ventil zumindest an einer Stelle des Ventilschaftes mit dem erfindungsgemäßen Verfahren beschichtet, das heißt die erfindungsgemäße Verschleißschutzschicht aufgebracht wird, wobei selbstverständlich klar ist, dass diese Verschleißschutzschicht auch am gesamten Ventil oder an anderen Stellen, beispielsweise an einem Ventilsitzring, aufgebracht werden kann. It has always been mentioned in the preceding paragraphs that the valve is coated with the method according to the invention at least at one point of the valve stem, that is, the wear protection layer according to the invention is applied, it being understood that this wear protection layer is also applied to the entire valve or to other locations, for example can be applied to a valve seat ring.
Die vorliegende Erfindung beruht weiter auf dem allgemeinen Gedanken, ein Ventil einer Brennkraftmaschine anzugeben, welches mit dem zuvor beschriebenen Verfahren an zumindest einer Stelle beschichtet wurde. Hierzu weist das erfindungsgemäße Ventil eine Nickel (Ni) aufweisende Haftschicht sowie eine darüber angeordnete Verschleißschutzschicht aus Nickel (Ni) und Borcarbid (B C) auf. Zur Oberflächenvergütung ist die Verschleißschutzschicht nachbearbeitet, beispielsweise poliert oder geschliffen. Mittels eines derartigen Ventils kann insbesondere auf die bislang in diesem Bereich eingesetzte und chromhaltige Verschleißschutzschicht verzichtet, jedoch die gleiche oder sogar eine noch bessere Verschleißbeständigkeit geschaffen werden. The present invention is further based on the general idea to provide a valve of an internal combustion engine, which has been coated at least one point by the method described above. For this purpose, the valve according to the invention has a nickel (Ni) adhesive layer and an overlying wear protection layer of nickel (Ni) and boron carbide (B C). For surface treatment, the wear protection layer is reworked, for example, polished or ground. By means of such a valve can be dispensed with in particular in the field previously used in this area and chromium-containing wear protection layer, however, the same or even better wear resistance can be created.
Erfindungsgemäß weist die Verschleißschutzschicht eine Schichtdicke d zwischen 5 μιτι und 15 μιτι auf. Bereits eine derartige dünne Verschleißschutzschicht ermöglicht dabei die Verschleißbeständigkeit des Ventils über seine gesamte Lebensdauer, wobei als Haftgrund bzw. Haftschicht für die Verschleißschutzschicht die darunter angeordnete Nickelschicht verwendet wird, welche eine zuverlässige Haftung der Verschleißschutzschicht auch auf Edelstahloberflächen ermöglicht. Diese Nickelzwischenschicht, die in einem Nickelchlorid-Elektrolyt aufgebracht wird, ist zwingend notwendig, insbesondere beim Einsatz von hochlegierten Edelstahlen wie beispielsweise X50. Ansonsten kann keine ausreichende Haftung der Nickeldispersionsschicht erzielt werden. According to the invention, the wear protection layer has a layer thickness d between 5 μm and 15 μm. Already such a thin wear protection layer allows the wear resistance of the valve over its entire life, being used as a primer or adhesive layer for the wear protection layer, the underlying nickel layer, which allows reliable adhesion of the wear protection layer on stainless steel surfaces. This nickel interlayer, which is applied in a nickel chloride electrolyte is imperative, especially when using high-alloy Stainless steels such as X50. Otherwise, sufficient adhesion of the nickel dispersion layer can not be achieved.
Weitere wichtige Merkmale und Vorteile der Erfindung ergeben sich aus den Unteransprüchen, aus der Zeichnung und aus der zugehörigen Figurenbeschreibung anhand der Zeichnung. Other important features and advantages of the invention will become apparent from the dependent claims, from the drawing and from the associated description of the figures with reference to the drawing.
Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale nicht nur in der jeweils angegebenen Kombination, sondern auch in anderen Kombinationen oder in Alleinstellung verwendbar sind, ohne den Rahmen der vorliegenden Erfindung zu verlassen. It is understood that the features mentioned above and those yet to be explained below can be used not only in the particular combination given, but also in other combinations or in isolation, without departing from the scope of the present invention.
Ein bevorzugtes Ausführungsbeispiel der Erfindung ist in der Zeichnung dargestellt und wird in der nachfolgenden Beschreibung näher erläutert. A preferred embodiment of the invention is illustrated in the drawing and will be explained in more detail in the following description.
Die einzige Figur 1 zeigt ein erfindungsgemäßes Ventil mit einer erfindungsgemäß darauf aufgebrachten Verschleißschutzschicht. The sole FIGURE 1 shows a valve according to the invention with a wear protection layer applied thereto according to the invention.
Entsprechend der Fig. 1 weist ein erfindungsgemäßes Ventil 1 einer im Übrigen nicht näher dargestellten Brennkraftmaschine 2 einen Ventilteller 3 sowie einen daran über eine Ventilkehle 4 angeschlossenen Ventilschaft 5 auf. Zumindest an einer Stelle im Bereich des Ventilschaftes 5, an welcher dieser in einer Ventilführung 6 geführt ist, ist das erfindungsgemäße Ventil 1 mit einer Verschleißschutzschicht 7 versehen. Die Ventilführung 6 kann dabei aus einem Sinterwerkstoff ausgebildet sein. Aufgrund der sehr guten Benetzbarkeit der Nickeldispersionsschicht mit Öl, ist der Verschleiß der Ventilführung deutlich reduziert im Vergleich zu einem mit Chrom beschichteten Ventilschaft. Weiterhin kann sich das B C (Borcarbid) bei hohen Temperaturen (380-420)°C und in Anwesenheit von Sauerstoff eine graphitähnliche Struktur (Bor(l)oxid) umwandeln. Zwischen der Ver- schleißschutzschicht 7 und dem Ventilschaft 5 ist dabei eine nickelhaltige Haftschicht 8 angeordnet. Erfindungsgemäß weist nun die Verschleißschutzschicht 7 Nickel (Ni) und Borcarbid (B C) auf, wodurch diese sowohl eine hohe chemische Beständigkeit als auch eine hohe Verschleißbeständigkeit besitzt. Um diese Verschleißbeständigkeit weiter steigern zu können, ist eine Oberfläche der Verschleißschutzschicht 7 nachbearbeitet, insbesondere poliert und/oder geschliffen. According to FIG. 1, a valve 1 according to the invention of an internal combustion engine 2, which is not further illustrated, has a valve disk 3 and a valve stem 5 connected thereto via a valve throat 4. At least at one point in the region of the valve stem 5, on which it is guided in a valve guide 6, the valve 1 according to the invention is provided with a wear protection layer 7. The valve guide 6 may be formed of a sintered material. Due to the very good wettability of the nickel dispersion layer with oil, the wear of the valve guide is significantly reduced compared to a chrome-coated valve stem. Furthermore, the BC (boron carbide) can transform at high temperatures (380-420) ° C and in the presence of oxygen a graphite-like structure (boron oxide). Between the Wear protection layer 7 and the valve stem 5 is a nickel-containing adhesive layer 8 is arranged. According to the invention, the wear protection layer 7 now comprises nickel (Ni) and boron carbide (BC), as a result of which it has both high chemical resistance and high wear resistance. In order to further increase this wear resistance, a surface of the wear-resistant layer 7 is reworked, in particular polished and / or ground.
Hergestellt wird das erfindungsgemäße Ventil 1 bzw. die darauf aufgebrachte Beschichtung wie folgt: The valve 1 according to the invention or the coating applied thereto is produced as follows:
Zunächst wird das Ventil 1 zumindest mit der zu beschichtenden Stelle, insbesondere im Bereich des Ventilschaftes 5, in ein Nickel (Ni) haltiges Reinbad als Haftvermittler getaucht, wodurch die Haftschicht 8 auf die Oberfläche des Ventilschaftes 5 aufgebracht wird. Diese Haftschicht 8 ist zur langanhaltenden und zuverlässigen Verbindung der Verschleißschutzschicht 7 mit dem Ventil 1 erforderlich. Anschließend wird das Ventil 1 zumindest mit der zu beschichtenden Stelle in ein Nickel (Ni) und Borcarbid (B C) oder in ein Nickel-Wolfram (Ni-W) oder Nickel-Eisen (Ni-Fe) und Borcarbid (B C) aufweisendes Bad getaucht, wodurch die eigentliche Verschleißschutzschicht 7 aufgebracht wird. Wiederum daran anschließend wird das Ventil 1 zumindest im Bereich der Verschleißschutzschicht 7 nachbearbeitet, beispielsweise poliert und/oder geschliffen. First, the valve 1 is dipped at least with the point to be coated, in particular in the region of the valve stem 5, in a nickel (Ni) -containing pure bath as a primer, whereby the adhesive layer 8 is applied to the surface of the valve stem 5. This adhesive layer 8 is required for long-lasting and reliable connection of the wear protection layer 7 with the valve 1. Subsequently, the valve 1 is immersed at least with the point to be coated in a bath having nickel (Ni) and boron carbide (BC) or in a nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (BC) , whereby the actual wear protection layer 7 is applied. Subsequently, the valve 1 is subsequently reworked at least in the region of the wear protection layer 7, for example polished and / or ground.
Das zur Herstellung der Verschleißschutzschicht 7 verwendete Bad weist dabei einen Borcarbidgehalt von 30 g/l bis 65 g/l, insbesondere einen Borcarbidgehalt von ca. 50 g/l auf, bei welchem festgestellt wurde, dass sich ein Verschleiß von nahezu Null ergibt und in repräsentativen Tests ein Materialübertrag bei lediglich 1/10 des Materialübertrags im Vergleich zur Verwendung einer chromhaltigen Verschleißschutzschicht liegt. Bei der Beurteilung der Verschleißbeständigkeit sind dabei insbesondere zwei Kennwerte von besonderer Bedeutung, zum einen der Verschleiß, also der Materialabtrag der Verschleißschutzschicht 7 selbst und zum anderen der sogenannte Materialübertrag, also der Transfer von Beschich- tungsmaterial in die Ventilführung 6. The bath used to produce the wear protection layer 7 has a boron carbide content of 30 g / l to 65 g / l, in particular a boron carbide content of about 50 g / l, which has been found to result in almost zero wear and in Representative tests a material transfer is only 1/10 of the material transfer compared to the use of a chromium-containing wear protection layer. In the evaluation of wear resistance, in particular two characteristic values are of particular importance, on the one hand the wear, ie the material removal of the wear protection layer 7 itself and, secondly, the so-called material transfer, ie the transfer of coating material into the valve guide 6.
Bei einer weiteren vorteilhaften Ausführungsform der erfindungsgemäßen Lösung kann auch ein Nickel (Ni) und Borcarbid (B C) aufweisendes Bad zur Herstellung der Verschleißschutzschicht 7 verwendet werden, wobei dieses Bad zusätzlich hexagonalem Bornitrid (h(BN)) aufweist. Der Bornitridgehalt (h(BN)) dieses Bades liegt dabei zwischen 10 g/l und 25 g/l, insbesondere zwischen 18 und 22 g/l, besonders bevorzugt ca. 20 g/l. Letztere Konzentration bzw. der zuletzt genannte Bornitridgehalt von ca. 20 g/l hat sich dabei besonders vorteilhaft bezüglich des Materialübertrags erwiesen. In a further advantageous embodiment of the solution according to the invention, a bath containing nickel (Ni) and boron carbide (B C) can also be used to produce the wear protection layer 7, this bath additionally having hexagonal boron nitride (h (BN)). The boron nitride content (h (BN)) of this bath is between 10 g / l and 25 g / l, in particular between 18 and 22 g / l, particularly preferably about 20 g / l. The latter concentration or the last-mentioned boron nitride content of about 20 g / l has proved to be particularly advantageous with respect to the material transfer.
Das Bad kann zusätzlich Hartstoffpartikel enthalten. Mindestens einer dieser Hartstoffpartikel weist dabei Siliziumcarbid (SiC), Wolframcarbid (WC), Titannitrid (TiN), Siliziumnitrid (Si3N ), kubisches Bornitrid (c-BN) oder Aluminiumoxid (AI2O3) auf oder besteht daraus. Die Hartstoffpartikel weisen üblicherweise einen Durchmesser auf, der im Mittel kleiner oder gleich 0,1 μιτι bis 3 μιτι, insbesondere von 0,8 μιτι bis 2,5 μιτι ist. Durch Zugabe von diversen Hartstoffpartikeln (z.B. TiN, SiC, WC oder anderen) kann die Verschleißbeständigkeit von galvanischen Schichtsystemen deutlich erhöht werden. Aufgrund der sehr geringen Partikeldurchmesser im Bereich von 0,1 bis 3 μιτι erzeugt man eine Einglättung (eine Art Polieren) des Gegenlaufpartners z.B. der Ventilführung. Die Verschleißschutzschicht 7 selbst besitzt eine Schichtdicke d, die zwischen 5 und 15 μιτι aufweist. The bath may additionally contain hard material particles. At least one of these hard material particles has or consists of silicon carbide (SiC), tungsten carbide (WC), titanium nitride (TiN), silicon nitride (Si 3 N), cubic boron nitride (c-BN) or aluminum oxide (Al 2 O 3). The hard material particles usually have a diameter which is on average less than or equal to 0.1 μιτι to 3 μιτι, in particular from 0.8 μιτι to 2.5 μιτι. By adding various hard particles (for example TiN, SiC, WC or others) the wear resistance of galvanic layer systems can be significantly increased. Due to the very small particle diameter in the range of 0.1 to 3 μιτι one creates a smoothing (a kind of polishing) of the Gegenlaufpartners e.g. the valve guide. The wear protection layer 7 itself has a layer thickness d, which has between 5 and 15 μιτι.
Mit der erfindungsgemäßen Verschleißschutzschicht 7 kann somit eine bislang in diesem Bereich eingesetzte und chromhaltige Verschleißschutzschicht ersetzt werden, was erhebliche Vorteile hinsichtlich der Unbedenklichkeit in Bezug auf Umwelt und Gesundheit und mit den sich daraus geänderten Kundenanforderun- gen bringt. Zudem kann mit einer derartigen und nunmehr nicht mehr chromhaltigen Verschleißschutzschicht 7 auch den Bedenken in Bezug auf die Verwendung von Chrom Rechnung getragen werden. Von besonderer Bedeutung ist dabei, dass die erfindungsgemäße Verschleißschutzschicht 7 eine extreme hohe Verschleißbeständigkeit sowie eine hohe chemische Beständigkeit aufweist und darüber hinaus einen Materialübertrag besitzt, der lediglich bei 1/10 des Materialübertrags bisheriger chromhaltiger Verschleißschutzschichten liegt. With the wear protection layer 7 according to the invention, it is therefore possible to replace a wear protection layer previously used in this area and containing chromium, which has considerable advantages with regard to the safety in terms of the environment and health and with the customer requirements changed as a result. brings. In addition, with such and now no longer chromium-containing wear protection layer 7 and the concerns regarding the use of chrome accounted for. Of particular importance is that the wear protection layer 7 of the invention has an extremely high wear resistance and high chemical resistance and also has a material transfer, which is only 1/10 of the material transfer of previous chromium-containing wear protection layers.

Claims

Patentansprüche claims
1. Verfahren zum Beschichten eines Ventils (1 ) einer Brennkraftmaschine (2), insbesondere einer Stelle eines Ventilschafts (5) des Ventils (1 ), bei dem 1. A method for coating a valve (1) of an internal combustion engine (2), in particular a point of a valve stem (5) of the valve (1), wherein
- das Ventil (1 ) zumindest mit der zu beschichtenden Stelle in ein Nickel (Ni) Reinbad als Haftvermittler getaucht wird,  - the valve (1) is dipped at least with the point to be coated in a nickel (Ni) pure bath as a primer,
- das Ventil (1 ) zumindest mit der zu beschichtenden Stelle in ein Nickel (Ni) und Borcarbid (B C) aufweisendes Bad oder in ein Nickel-Wolfram (Ni-W) oder Nickel-Eisen (Ni-Fe) und Borcarbid (B C) aufweisendes Bad getaucht wird, - The valve (1) at least with the point to be coated in a nickel (Ni) and boron carbide (BC) exhibiting bath or in a nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (BC) bath is dipped,
- das Ventil (1 ) zumindest an der zu beschichtenden Stelle nachbearbeitet wird. - The valve (1) is reworked at least at the point to be coated.
2. Verfahren nach Anspruch 1 , erste Alternative, 2. Method according to claim 1, first alternative,
dadurch gekennzeichnet, characterized,
dass ein Nickel (Ni) und Borcarbid (B C) aufweisendes Bad verwendet wird, mit einem Borcarbidgehalt von 30 g/l bis 65 g/l, insbesondere von 50 g/l. that a bath comprising nickel (Ni) and boron carbide (B C) is used, having a boron carbide content of from 30 g / l to 65 g / l, in particular of 50 g / l.
3. Verfahren nach Anspruch 1 , erste Alternative oder nach Anspruch 2, dadurch gekennzeichnet, 3. The method according to claim 1, first alternative or claim 2, characterized
dass das Ventil (1 ) zumindest mit der zu beschichtenden Stelle in ein Nickel (Ni), Borcarbid (B C) und hexagonales Bornitrid (h(BN)) aufweisendes Bad getaucht wird. the valve (1) is immersed, at least with the point to be coated, in a bath comprising nickel (Ni), boron carbide (B C) and hexagonal boron nitride (h (BN)).
4. Verfahren nach einem der Ansprüche 1 bis 3, 4. The method according to any one of claims 1 to 3,
dadurch gekennzeichnet, characterized,
dass ein Nickel (Ni), Borcarbid (B C) und hexagonalem Bornitrid (h(BN)) aufweisendes Bad verwendet wird, mit einem Bornitridgehalt (h(BN)) von 10g/I bis 25 g/l, insbesondere mit einem Bornitridgehalt (h(BN)) von 18 g/l bis 22 g/l, besonders bevorzugt mit einem Bornitridgehalt (h(BN)) von 20 g/l. that a bath containing nickel (Ni), boron carbide (BC) and hexagonal boron nitride (h (BN)) is used, with a boron nitride content (h (BN)) of 10 g / l to 25 g / l, in particular with a boron nitride content (h (BN)) of 18 g / l to 22 g / l, particularly preferably with a boron nitride content (h (BN)) of 20 g / l.
5. Verfahren nach einem der Ansprüche 1 bis 4, 5. The method according to any one of claims 1 to 4,
dadurch gekennzeichnet, characterized,
dass Bad zusätzlich Hartstoffpartikel enthält. that bath additionally contains hard material particles.
6. Verfahren nach Ansprüche 5, 6. The method according to claims 5,
dadurch gekennzeichnet, characterized,
dass mindestens eines der Hartstoffpartikel aus Siliziumcarbid (SiC) oder Wolf- ramcarbid (WC) oder Titannitrid (TiN) oder Siliziumnitrid (Si3N ) oder kubisches Bornitrid (c-BN) oder Aluminiumoxid (AI2O3) besteht. at least one of the hard material particles consists of silicon carbide (SiC) or tungsten carbide (WC) or titanium nitride (TiN) or silicon nitride (Si3N) or cubic boron nitride (c-BN) or aluminum oxide (Al2O3).
7. Verfahren nach Anspruch 5 oder 6, 7. The method according to claim 5 or 6,
dadurch gekennzeichnet, characterized,
das die Hartstoffpartikel einen Durchmesser aufweisen, der im Mittel kleiner oder gleich 0,1 μιτι bis 3 μιτι, insbesondere von 0,8 μιτι bis 2,5 μιτι ist. that the hard material particles have a diameter which is on average less than or equal to 0.1 μιτι to 3 μιτι, in particular from 0.8 μιτι to 2.5 μιτι.
8. Verfahren nach einem der Ansprüche 1 bis 7, 8. The method according to any one of claims 1 to 7,
dadurch gekennzeichnet, characterized,
dass das Ventil (1 ) zumindest an der zu beschichtenden Stelle poliert und/oder geschliffen wird. the valve (1) is polished and / or ground at least at the point to be coated.
9. Ventil (1 ) einer Brennkraftmaschine (2), mit zumindest einer nach dem Verfahren nach einem der Ansprüche 1 bis 8 beschichteten Stelle, an der 9. Valve (1) of an internal combustion engine (2), with at least one coated by the method according to one of claims 1 to 8 point at the
- das Ventil (1 ) eine Nickel (Ni) aufweisende Haftschicht (8) aufweist,  - the valve (1) has a nickel (Ni) having adhesive layer (8),
- das Ventil (1 ) eine Nickel (Ni) und Borcarbid (B C) oder eine Nickel-Wolfram (Ni-W) oder Nickel-Eisen (Ni-Fe) und Borcarbid (B C) aufweisende Verschleißschutzschicht (7) aufweist, das Ventil (1 ) nachbearbeitet ist. - The valve (1) has a nickel (Ni) and boron carbide (BC) or a nickel-tungsten (Ni-W) or nickel-iron (Ni-Fe) and boron carbide (BC) having wear protection layer (7), the valve (1) is reworked.
10. Ventil nach Anspruch 9, 10. Valve according to claim 9,
dadurch gekennzeichnet, characterized,
dass das Ventil (1 ) zumindest im Bereich der Verschleißschutzschicht (7) poliert und/oder geschliffen ist. the valve (1) is polished and / or ground, at least in the region of the wear protection layer (7).
11. Ventil nach Anspruch 9 oder 10, 11. Valve according to claim 9 or 10,
dadurch gekennzeichnet, characterized,
dass die Verschleißschutzschicht (7) eine Schichtdicke d zwischen 5 μιτι < d < 15 μιτι aufweist. that the wear protection layer (7) has a layer thickness d between 5 μιτι <d <15 μιτι.
12. Brennkraftmaschine (2) mit zumindest einem Ventil (1 ) nach einem der Ansprüche 9 bis 11. 12. Internal combustion engine (2) with at least one valve (1) according to one of claims 9 to 11.
13. Brennkraftmaschine (2) nach Anspruch 12, 13. Internal combustion engine (2) according to claim 12,
dadurch gekennzeichnet, characterized,
dass zumindest eine Ventilführung (6) zur Führung des Ventils (1 ) aus einem Sinterwerkstoff hergestellt ist. in that at least one valve guide (6) for guiding the valve (1) is made of a sintered material.
PCT/EP2016/059295 2015-06-09 2016-04-26 Method for coating a valve of an internal combustion engine WO2016198205A1 (en)

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