EP2826985A2 - Injection valve for an internal combustion engine and method for producing an injection valve - Google Patents

Injection valve for an internal combustion engine and method for producing an injection valve Download PDF

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Publication number
EP2826985A2
EP2826985A2 EP14174075.3A EP14174075A EP2826985A2 EP 2826985 A2 EP2826985 A2 EP 2826985A2 EP 14174075 A EP14174075 A EP 14174075A EP 2826985 A2 EP2826985 A2 EP 2826985A2
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EP
European Patent Office
Prior art keywords
oxide layer
oxide
injection valve
valve head
valve
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP14174075.3A
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German (de)
French (fr)
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EP2826985A3 (en
EP2826985B1 (en
Inventor
Robert Ukropec
Clemens Maria Verpoort
Oliver Berkemeier
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Ford Global Technologies LLC
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Ford Global Technologies LLC
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    • 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
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • 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
    • 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
    • C23C28/042—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 including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • 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
    • F02M1/00—Carburettors with means for facilitating engine's starting or its idling below operational temperatures
    • F02M1/16—Other means for enriching fuel-air mixture during starting; Priming cups; using different fuels for starting and normal operation
    • F02M1/18—Enriching fuel-air mixture by depressing float to flood carburettor
    • 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
    • F02M61/06—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 the valves being furnished at seated ends with pintle or plug shaped extensions
    • 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
    • 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
    • F02M61/168—Assembling; Disassembling; Manufacturing; Adjusting
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S239/00—Fluid sprinkling, spraying, and diffusing
    • Y10S239/19—Nozzle materials

Definitions

  • the present invention relates to an injection valve for an internal combustion engine, in particular for an internal combustion engine of a motor vehicle according to the preamble of claim 1, and to a method for producing an injection valve according to claim 6.
  • Internal combustion engines serve to convert the energy contained in a fuel into kinetic energy.
  • the internal combustion engine has at least one combustion chamber in which the fuel is burned. The resulting volumetric expansion during combustion is then translated into a rotational rotary motion.
  • the fuel is previously mixed with ambient air, in particular with the oxygen (O 2 ) contained therein.
  • the internal combustion engines differ essentially in spark igniter and diesel.
  • gasoline engines are considered as external igniters, while diesel engines are referred to as compression-ignition.
  • diesel engines are referred to as compression-ignition.
  • gasoline engines located in the combustion chamber mixture is first compressed and then ignited, for example via a spark plug.
  • compression concentrates on that of the combustion chamber supplied air, which thereby undergoes a rapid increase in temperature. The temperature generated in this case is sufficient to ignite the subsequently injected into the compressed air so diesel fuel.
  • liquid form such as gasoline, diesel, liquefied petroleum gas (LPG) or liquefied natural gas (LNG) are also used as gas fuels, for example in the form of compressed natural gas (CNG) or hydrogen (H 2 ).
  • LPG liquefied petroleum gas
  • LNG liquefied natural gas
  • Other alternative fuels include, for example, ethanol (C 2 H e O) or methanol (CH 4 O).
  • valve head Since the injectors have to bring the fuel directly into the combustion chamber of the internal combustion engine, the valve head is directly exposed to the heat generated during the combustion process. In this case, the valve head is either arranged in sections in the combustion chamber or at least directly facing it. In any case, the valve head is charged directly with the heat of combustion. In particular, the valve head in this installation position is subject to special requirements. In addition to the high temperatures, it is also sometimes necessary to withstand high injection pressures and temperature shocks. In addition, corrosive effects due to the combustion products formed during combustion must be taken into account, which play a major role in particular when using alternative fuels.
  • the fuel injection valve which serves the direct injection of a fuel such as gasoline or diesel in the combustion chamber of an internal combustion engine.
  • the fuel injection valve has a valve head which has at least one outlet opening for the fuel.
  • the aim is to maintain the spray parameters of the outlet, which can be negatively affected by any deposits.
  • the coating is shown.
  • the materials proposed to form the coating are classified into three groups depending on the properties to be achieved.
  • a first group of cobalt or nickel oxides as well as oxides of alloys of said metals is said to prevent catalytic conversion (combustion) of already deposited soot particles and deposition of carbon particles.
  • Precious metals such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt) as well as alloys of these metals among themselves or with other metals are also included in this first group.
  • a second group of metals is intended to alter the wetting behavior on the surface of the valve head so that the fuel droplets can bead off and be entrained by the surrounding flow.
  • metal-containing or metal-free carbon layers and fluorine-containing layers or sapphire layers are counted.
  • the third and last group is seen in the use of nitride layers such as titanium nitride (TiN) or chromium nitride (CrN) as well as in oxide layers such as tantalum (TaO) or titanium oxide (TiO). Their use is intended to prevent a reaction layer on the valve head.
  • the DE 42 22 137 B4 is also directed to a fuel injector which is applicable to diesel engines.
  • the fuel injector has a Nozzle head with at least one spray hole.
  • a coating extending into the injection hole is provided.
  • a modification and / or reduction of the effective cross section of the injection hole is achieved, which narrows frustoconically to the outlet side.
  • a hard material such as chromium (Cr), nickel (Ni), nickel-phosphorus, nickel-boron or nickel-cobalt-boron and aluminum oxide (Al 2 O 3 ), chromium oxide (Cr 2 O 3 ) , Titanium oxide (TiO 2 ), chromium carbide (Cr 3 C 2 ), silicon dioxide (SiO 2 ), (AlSi), (NiCr), (WTi) or (WC).
  • the JP 2005-155618 A discloses a method for uniformly forming a layer of titanium oxide (TiO) in an injector of an injector for an internal combustion engine. Said layer is intended to prevent or at least reduce any accumulation of carbon deposits.
  • it is proposed first to immerse at least one section of the injection nozzle in a film-forming undiluted solution with titanium ammonium fluoride (NH 4 ) 2 TiF 6 and boric acid H 3 BO 3 .
  • titanium oxide (TiO 2) is deposited on the surface of a valve seat and the inside of the injection nozzle to form a titanium oxide coating.
  • the accumulation of deposits on the valve heads of injection valves should therefore be reduced essentially for the reason that the structural spray properties of the outlet openings should be maintained as long as possible.
  • this has not hitherto taken into account the additional emissions-related disadvantages resulting from the deposits.
  • said coating becomes thicker with increasing operating time, whereby the emissions of volatile organic substances (HC emissions) increase. This is due to uncontrolled burns of any residues of fuel. These are ignited in an undesirable manner via the injection valve, whose with the Covered valve head still smoldering at the end of a combustion cycle; comparable to a glow plug.
  • the object of the invention is to improve an injection valve for an internal combustion engine, in particular for an internal combustion engine of a motor vehicle, in such a way that the emissions of fuel during the combustion process are permanently reduced in view of the volatile organic substances (HC emissions) , Furthermore, a method for producing an injection valve is to be shown, by which an injection valve with permanently reduced emissions during operation, in particular those with volatile organic substances (HC emissions) can be made.
  • HC emissions volatile organic substances
  • an injection valve for an internal combustion engine is shown.
  • This may preferably be an internal combustion engine of a motor vehicle.
  • the injection valve conventionally comprises a valve body with a valve head.
  • the valve head is provided for the injection of fuel into the combustion chamber of the internal combustion engine.
  • the valve head is designed so that this in the installed state of the injection valve in the Internal combustion engine is at least partially disposed in the combustion chamber. If the valve head as flush as possible with those, the combustion chamber bounding surfaces to be formed, the valve head is at least directly facing the combustion chamber. Furthermore, said valve head is at least partially coated with a first oxide layer.
  • a catalytic second oxide layer of cerium oxide (CeO 2 ) is arranged above the first oxide layer.
  • the second oxide layer may also consist of praseodymium oxide (PrO 2 ) or zirconium oxide (ZrO 2 ).
  • the second oxide layer may also be composed of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) or cerium oxide (CeO 2) and zirconia (ZrO 2).
  • a composition of the second oxide layer of praseodymium oxide (PrO 2 ) and zirconium oxide (ZrO 2 ) is also conceivable.
  • the first oxide layer can be formed from titanium oxide (TiO 2 ).
  • the first oxide layer may also consist of aluminum oxide (Al 2 O 3 ).
  • the respective oxide compound of titanium (Ti) and / or porous ceramic oxide layer of aluminum (Al) are ideal supports for the second catalytic oxide layer.
  • the first oxide layer preferably has a thickness of 10.0 to 20.0 ⁇ m.
  • aluminum oxide (Al 2 O 3 ) is characterized by its high temperature resistance, its high surface area and its advantageous acid-base properties and by its good interaction with other metals as a support material for catalysts.
  • the first oxide layer is impregnated with copper oxide (CuO).
  • the second oxide layer may be impregnated with copper oxide.
  • both the first oxide layer and the second oxide layer may be impregnated with copper oxide (CuO) as well.
  • the advantage of impregnation with copper oxide (CuO) is the elimination or reduction, up to the prevention of deposits on the thus coated valve head.
  • the combustion of soot in the foreground is due in particular to the catalyst consisting of cerium oxide (CeO 2 ) and copper oxide (CuO) or praseodymium oxide (PrO 2 ) and copper oxide (CuO) and deposited on the valve head from these compounds. Said impregnation enables a further reduction of the light-off temperature of combustible constituents.
  • the first oxide layer and / or the second oxide layer may be provided with platinum (Pt) and / or another element from the group may be impregnated by platinum metals.
  • the platinum metals are in addition to platinum (Pt) in particular ruthenium (Ru) and / or osmium (Os) and / or rhodium (Rh) and / or iridium (Ir) and / or palladium (Pd).
  • the advantage resulting from the impregnation with one or more of the aforementioned elements is also an elimination or reduction, up to the prevention of deposits on the thus coated valve head.
  • a further reduction in the light-off temperature of combustible constituents can be achieved.
  • At least the valve head of the injection valve is formed at least partially from a powder metallurgical Al-Si material (PEAK S250).
  • the Al-Si material of the manufacturer PEAK is an aluminum material AlSi 20 Fe 5 Ni 2 , which has a very high strength and rigidity compared to conventional aluminum alloys.
  • tensile strengths of up to 750 N / mm 2 can be achieved.
  • the high proportion of primarily precipitated silicon causes a natural surface.
  • the precipitated on the surface silicon particles form a uniform layer thickness from 4.0 to 5.0 ⁇ m.
  • the valve head produced at least partially from S250 already has a high wear resistance without a coating.
  • the aluminum material AlSi 20 Fe 5 Ni 2 used as valve head serves as substrate for the coating with the elements and / or compounds according to the invention.
  • the valve head can be formed at least partially from a titanium alloy (Ti6Al4V).
  • Ti6Al4V a titanium alloy
  • the titanium alloy has a more difficult workability, especially when introducing the required outlet openings.
  • the second oxide layer of cerium oxide (CeO 2 ) on the titanium alloy is less effective than on the Al-Si material according to the invention.
  • the present invention shows an improved over the prior art injection valve in the region of its valve head.
  • the inventive surface of the valve head prevents deposition of liquid fuel in the form of droplets, which otherwise dry on the surface of the valve head. Here they leave after some time tar and / or coal deposits, which are not easy to remove.
  • Such pads have a negative effect on the emissions of the internal combustion engine in operation.
  • the effect of the inventive coating of the valve head as a catalyst causes the said droplets to evaporate on the surface of the valve head and thus can not form deposits.
  • a method is shown with which a previously shown improved injection valve for an internal combustion engine, in particular for an internal combustion engine of a motor vehicle can be produced.
  • Said injection valve comprises a valve body with a valve head.
  • the valve head is designed to be arranged in the internal combustion engine at least in sections in a combustion chamber of the internal combustion engine in the installed state of the injection valve, or at least partially facing it be.
  • the valve head is at least partially coated with a first oxide layer.
  • a second oxide layer is applied as a washcoat over the first oxide layer.
  • the second oxide layer according to the invention applied as washcoat consists of cerium oxide (CeO 2 ).
  • the second oxide layer may also consist of praseodymium oxide (PrO 2 ) or zirconium oxide (ZrO 2 ).
  • the applied as a washcoat second oxide layer may also be composed of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) or cerium oxide (CeO 2) and zirconia (ZrO 2).
  • a composition of the second oxide layer of praseodymium oxide (PrO 2 ) and zirconium oxide (ZrO 2 ) is also conceivable.
  • this is initially present as a powder suspension.
  • This powder suspension is then applied, for example, as an aqueous suspension to the substrate in the form of the already coated with the first oxide layer valve head and dried. By subsequent calcination, the suspension thus applied is activated.
  • the first oxide layer is formed from titanium oxide (TiO 2 ).
  • the first oxide layer may be formed of alumina (Al 2 O 3 ).
  • the first oxide layer is preferably applied to the surface of the valve head at least in regions with a thickness of 10.0 to 20.0 ⁇ m.
  • the first oxide layer can be applied to the valve head by means of a micro arc oxidation (MAO).
  • the first Oxide layer can also be applied by a plasma electrolytic oxidation (PEO) on the valve head.
  • the Micro Arc Oxidation improves the surface properties of the valve head, increasing its hardness and wear resistance, among other things.
  • the first oxide layer is advantageously converted into a dense, atomically adhering ceramic layer.
  • the first oxide layer is impregnated with copper oxide (CuO).
  • the second oxide layer can be impregnated with copper oxide.
  • both the first oxide layer and the second oxide layer may be impregnated with copper oxide (CuO) as well.
  • the first oxide layer and / or the second oxide layer are provided with platinum (Pt) and / or another element from the group of platinum metals can / can be impregnated.
  • the platinum metals are in addition to platinum (Pt) in particular ruthenium (Ru) and / or osmium (Os) and / or rhodium (Rh) and / or iridium (Ir) and / or palladium (Pd).
  • At least the valve head of the injection valve is formed at least partially from a powder metallurgical Al-Si material (PEAK S250).
  • PEAK S250 powder metallurgical Al-Si material
  • the Osprey method for spray compacting In this case, the melt of the Al-Si material can be applied via a nozzle to a cooled copper plate. The spray-compacted bolts thus formed are then further processed by extrusion into rods or tubes.
  • a high-temperature aluminum eg PLM908 Powder Light Metals can be used.
  • the resulting aluminum strips are then compacted and extruded to produce semi-finished products.
  • the rapid rotation of the copper wheel cools the melt down so quickly that it solidifies immediately. Due to the high rotational speed of the copper wheel of the strand thus produced is then thrown off.
  • the advantage of this method consists in obtaining a preferred microstructure of the valve head which can be produced in this way.
  • the Al-Si material of the manufacturer PEAK is an aluminum material AlSi 20 Fe 5 Ni 2 , which has a very high strength and rigidity compared to conventional aluminum alloys.
  • the valve head can be formed at least partially from a titanium alloy (Ti6Al4V).
  • Ti6Al4V titanium alloy
  • melt spinning is also proposed for this purpose.
  • Fig. 1 is a schematic representation of an injection valve 1 according to the invention can be seen.
  • Said injection valve 1 is intended for use in an internal combustion engine, not shown.
  • the internal combustion engine may in particular be an internal combustion engine of a motor vehicle.
  • a portion of a wall 2 of a cylinder head 3 of the internal combustion engine not shown is indicated, through which the injection valve 1 is arranged.
  • a partial region of the injection valve 1 protrudes into a combustion chamber 4 of the internal combustion engine.
  • the injection valve 1 essentially comprises a valve body 5.
  • the combustion chamber 4 facing, in particular at least partially arranged in this section of the valve body 5 has a valve head 6.
  • the valve head 6 is formed at least partially from a powder metallurgical Al-Si material (PEAK S250) or from a titanium alloy (Ti 6 Al 4 V).
  • PEAK S250 powder metallurgical Al-Si material
  • Ti 6 Al 4 V titanium alloy
  • the dotted lines extending in a longitudinal direction a of the injection valve 1 serve to illustrate a channel 7 within the injection valve 1. Through this channel 7, a fuel (not shown) can be injected into the combustion chamber 4 via the injection valve 1.
  • At least one end face 8 of the valve head 6 is indicated with a first oxide layer 9 and a second oxide layer 10 arranged on the first oxide layer 9.
  • the first oxide layer 9 is formed from titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ).
  • the second oxide layer consists of cerium oxide (CeO 2 ).
  • the second oxide layer may also consist of praseodymium oxide (PrO 2 ) or zirconium oxide (ZrO 2 ).
  • the applied as a washcoat second oxide layer may also be composed of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) or cerium oxide (CeO 2) and zirconia (ZrO 2).
  • a composition of the second oxide layer of praseodymium oxide (PrO 2 ) and zirconium oxide (ZrO 2 ) is also conceivable.
  • first oxide layer 9 and / or the second oxide layer 10 are impregnated in a manner not shown in detail with copper oxide (CuO).
  • a further impregnation of the first oxide layer 9 and / or the second oxide layer 10 is further given by at least one or more elements also not shown in detail from the group of platinum metals.
  • Said group consists of ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt).
  • Fig. 2 shows the injection valve 1 from Fig. 1
  • any hints of the wall 2 of the cylinder head 3 and the outside of the combustion chamber 4 were located and in Fig. 1 shown end portion of the injection valve 1 omitted.
  • the valve head 6 has a plurality of outlet openings 11, visible from the outside in this view, from which the fuel can enter the combustion chamber 4 in a manner not shown in detail.
  • the outlet openings 11 are distributed with a number of six at a radially equal distance from the central longitudinal axis a of the injection valve 1 around it. In this case, they have a constant distance below each other, so that they are each offset by an equal angle b to each other.
  • Fig. 3 a diagram is shown with measurement results of an experiment. Within the diagram, two curves c, d can be seen. From the two curves c, d, a weight e of deposited on the valve head 6 soot emerges, based on its initial initial weight. Said soot is oxidized over time, so that its weight e decreases. The curves c, d are plotted against a temperature f in ° C. While a first curve c shown by a solid line shows the measurement results on a normal uncoated valve head 6, the remaining curve d shown with a broken line shows the measurement results on a valve head 6 coated and impregnated according to the invention.
  • This diagram is used to represent the improved combustion of soot on the with a catalytic second oxide layer 10 made of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) coated valve head 6.
  • a catalytic second oxide layer 10 made of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) coated valve head 6.
  • CeO 2 cerium oxide
  • PrO 2 praseodymium oxide
  • Valve head 6 with the first oxide layer 9 and the second oxide layer 10 of cerium oxide (CeO 2 ) and praseodymium oxide (PrO 2 ) coated and impregnated with copper oxide (CuO).
  • the copper oxide (CuO) deposits only in the second oxide layer 10.
  • the soot shown in the first curve c is synthetic soot, which is more stable compared to diesel and gasoline soot and burns at higher temperatures.
  • the combustion of soot in the first curve c above 70 ° C lower temperatures significantly for the combustion of soot on ceria (CeO 2 ) and praseodymium oxide (PrO 2 ) containing catalyst of copper oxide (CuO).
  • the shown measurement results in Fig. 3 come from test results on the combustion of synthetic soot in a laboratory, which was obtained via a thermogravimetric analyzer (TGA).
  • the carbon black used was made by Hiden, UK from a quartz tube. For this purpose, about 40.0 milligrams of carbon black were mixed with 120.0 milligrams of silicon carbide (SiC). Furthermore, alternatively, a catalyst was added. Subsequently, the thus prepared valve head was placed in the basket of the thermogravimetric analyzer (TGA). The sample from the valve head was surrounded by 8% oxygen (O 2 ). Subsequently, the sample was heated to 800 ° C with a temperature increase of 10 ° C per minute. The resulting reaction gases were measured by a mass spectrometer.

Abstract

Die Erfindung betrifft ein Einspritzventil (1) für eine Brennkraftmaschine. Das Einspritzventil (1) umfasst einen Ventilkörper (5) mit einem Ventilkopf (6), wobei der Ventilkopf (6) dazu ausgebildet ist, um zumindest abschnittsweise in einem Brennraum (4) der Brennkraftmaschine angeordnet oder diesem zumindest unmittelbar zugewandt zu sein. Weiterhin ist der Ventilkopf (6) wenigstens bereichsweise mit einer ersten Oxid-Schicht (9) beschichtet. Erfindungsgemäß ist über der ersten Oxid-Schicht (9) eine zweite Oxid-Schicht (10) aus Ceroxid (CeO2) und/oder Praseodymoxid (PrO2) und/oder Zirconiumoxid (ZrO2) angeordnet. Weiterhin wird ein Verfahren zur Herstellung eines solchen Einspritzventils (1) aufgezeigt. Erfindungsgemäß wird hierzu die über der ersten Oxid-Schicht (9) anzuordnende zweite Oxid-Schicht (10) aus Ceroxid (CeO2) und/oder Praseodymoxid (PrO2) und/oder Zirconiumoxid (ZrO2) als Washcoat aufgebracht.

Figure imgaf001
The invention relates to an injection valve (1) for an internal combustion engine. The injection valve (1) comprises a valve body (5) with a valve head (6), wherein the valve head (6) is designed to be at least partially disposed in a combustion chamber (4) of the internal combustion engine or at least directly facing it. Furthermore, the valve head (6) is at least partially coated with a first oxide layer (9). According to the invention, a second oxide layer (10) of cerium oxide (CeO 2 ) and / or praseodymium oxide (PrO 2 ) and / or zirconium oxide (ZrO 2 ) is arranged above the first oxide layer (9). Furthermore, a method for producing such an injection valve (1) is shown. According to the invention, the second oxide layer (10) of cerium oxide (CeO 2 ) and / or praseodymium oxide (PrO 2 ) and / or zirconium oxide (ZrO 2 ) to be arranged above the first oxide layer (9) is applied as a washcoat for this purpose.
Figure imgaf001

Description

Die vorliegende Erfindung betrifft ein Einspritzventil für eine Brennkraftmaschine, insbesondere für eine Brennkraftmaschine eines Kraftfahrzeugs nach dem Oberbegriff des Anspruchs 1 sowie ein Verfahren zur Herstellung eines Einspritzventils nach Anspruch 6.The present invention relates to an injection valve for an internal combustion engine, in particular for an internal combustion engine of a motor vehicle according to the preamble of claim 1, and to a method for producing an injection valve according to claim 6.

Brennkraftmaschinen dienen dazu, die in einem Kraftstoff enthaltene Energie in Bewegungsenergie umzuwandeln. Hierzu weist die Brennkraftmaschine wenigstens einen Brennraum auf, in dem der Kraftstoff verbrannt wird. Die bei der Verbrennung entstehende Volumenausdehnung wird anschließend in eine rotatorische Drehbewegung übersetzt. Um ein zündfähiges und effizientes Gemisch für den Verbrennungsvorgang zu erhalten, wird der Kraftstoff zuvor mit Umgebungsluft, insbesondere mit dem darin enthaltenen Sauerstoff (O2) vermischt.Internal combustion engines serve to convert the energy contained in a fuel into kinetic energy. For this purpose, the internal combustion engine has at least one combustion chamber in which the fuel is burned. The resulting volumetric expansion during combustion is then translated into a rotational rotary motion. In order to obtain an ignitable and efficient mixture for the combustion process, the fuel is previously mixed with ambient air, in particular with the oxygen (O 2 ) contained therein.

War es insbesondere bei Kraftfahrzeugen bis vor einiger Zeit noch üblich, das gewünschte Gemisch mittels eines Vergasers außerhalb des Brennraums bereitzustellen, herrschen heute moderne Einspritzsysteme vor. Auf diese Weise findet die Gemischbildung nunmehr nahezu ausschließlich innerhalb des Brennraums statt. Bei der hierfür eingesetzten Direkteinspritzung werden Einspritzventile verwendet, mit denen der Kraftstoff in genau dosierter Menge direkt in den mit Luft befüllten Brennraum eingespritzt wird. Während des Einspritzens findet die Zerstäubung des Kraftstoffs in der Luft innerhalb des Brennraums statt, um eine sichere und insbesondere emissionsarme Verbrennung zu erhalten.Whereas it was still customary, especially in motor vehicles until some time ago, to provide the desired mixture by means of a carburetor outside the combustion chamber, modern injection systems prevail today. In this way, the mixture formation now takes place almost exclusively within the combustion chamber. In the direct injection used for this injection valves are used with which the fuel is injected in exactly metered amount directly into the air-filled combustion chamber. During injection, the atomization of the fuel in the air takes place within the combustion chamber in order to obtain a safe and, in particular, low-emission combustion.

Je nach verwendetem Kraftstoff unterscheiden sich die Brennkraftmaschinen im Wesentlichen in Fremdzünder und Selbstzünder. Dabei gelten Ottomotoren als Fremdzünder, während Dieselmotoren als Selbstzünder bezeichnet werden. Bei Ottomotoren wird das im Brennraum befindliche Gemisch zunächst verdichtet und anschließend, beispielsweise über eine Zündkerze, gezündet. Demgegenüber konzentriert sich bei Dieselmotoren die Verdichtung auf die dem Brennraum zugeführte Luft, welche hierdurch einen raschen Temperaturanstieg erfährt. Die dabei erzeugte Temperatur ist ausreichend, um den anschließend in die so komprimierte Luft einzuspritzenden Diesel-Kraftstoff zu entzünden.Depending on the fuel used, the internal combustion engines differ essentially in spark igniter and diesel. In this case, gasoline engines are considered as external igniters, while diesel engines are referred to as compression-ignition. In gasoline engines located in the combustion chamber mixture is first compressed and then ignited, for example via a spark plug. In contrast, in diesel engines, compression concentrates on that of the combustion chamber supplied air, which thereby undergoes a rapid increase in temperature. The temperature generated in this case is sufficient to ignite the subsequently injected into the compressed air so diesel fuel.

Neben den bei Kraftfahrzeugen in flüssiger Form mitgeführten Kraftstoffen wie beispielsweise Benzin, Diesel, Flüssiggas (= Autogas, LPG) oder Flüssigerdgas (LNG) finden auch als Gas vorliegende Kraftstoffe Verwendung, beispielsweise in Form von verdichtetem Erdgas (CNG) oder von Wasserstoff (H2). Als weitere alternative Kraftstoffe sind beispielsweise Ethanol (C2HeO) oder Methanol (CH4O) zu nennen.In addition to the fuels carried in vehicles in liquid form such as gasoline, diesel, liquefied petroleum gas (LPG) or liquefied natural gas (LNG) are also used as gas fuels, for example in the form of compressed natural gas (CNG) or hydrogen (H 2 ). Other alternative fuels include, for example, ethanol (C 2 H e O) or methanol (CH 4 O).

Da die Einspritzventile den Kraftstoff direkt in den Brennraum der Brennkraftmaschine einbringen müssen, ist deren Ventilkopf unmittelbar der beim Verbrennungsprozess entstehenden Hitze ausgesetzt. Hierbei ist der Ventilkopf entweder abschnittsweise in dem Brennraum angeordnet oder diesem zumindest unmittelbar zugewandt. In jedem Fall wird der Ventilkopf dabei direkt mit der Verbrennungshitze beaufschlagt. So ist insbesondere der Ventilkopf in dieser Einbaulage besonderen Anforderungen ausgesetzt. Neben den hohen Temperaturen gilt es ferner mitunter hohen Einspritzdrücken und Temperaturschocks Stand zu halten. Zudem sind korrosive Einflüsse durch die bei der Verbrennung entstehenden Verbrennungsprodukte zu berücksichtigen, welche insbesondere bei der Verwendung alternativer Kraftstoffe eine große Rolle spielen.Since the injectors have to bring the fuel directly into the combustion chamber of the internal combustion engine, the valve head is directly exposed to the heat generated during the combustion process. In this case, the valve head is either arranged in sections in the combustion chamber or at least directly facing it. In any case, the valve head is charged directly with the heat of combustion. In particular, the valve head in this installation position is subject to special requirements. In addition to the high temperatures, it is also sometimes necessary to withstand high injection pressures and temperature shocks. In addition, corrosive effects due to the combustion products formed during combustion must be taken into account, which play a major role in particular when using alternative fuels.

Trotz der hohen Belastungen muss ein solches Einspritzventil insbesondere bei Kraftfahrzeugen einen sicheren Betrieb ermöglichen. Dies unabhängig von den Fahrzyklen und der Fahrleistung des Fahrzeugs sowie den jeweiligen klimatischen Bedingungen und dem verwendeten Kraftstoff. Bei der Wahl geeigneter Werkstoffe für derartige Einspritzventile wird daher wenigstens für den hoch belasteten Ventilkopf zumeist auf einen rostfreien austenitischen Stahl zurückgegriffen.Despite the high loads, such an injection valve must enable safe operation, especially in motor vehicles. This is independent of the driving cycles and the driving performance of the vehicle as well as the respective climatic conditions and the fuel used. When choosing suitable materials for such injectors, therefore, at least for the highly loaded valve head is usually resorted to a stainless austenitic steel.

Bei der Verwendung besagter Einspritzventile ist nach einer bestimmten Betriebszeit festzustellen, dass sich einige der Verbrennungsprodukte an dem Ventilkopf ablagern. In diesem Zusammenhang ist bekannt, dass sich eine solche Ablagerung eher und schneller auf der die austenitische Stahloberfläche schützenden Passivschicht aus Chromoxid (Cr203) abscheidet als beispielsweise auf einer Oberfläche aus Kupfer (Cu) oder Messing (CuZn). Bei der Ablagerung handelt es sich zumeist um Ruß und insbesondere um Ölkohle.When using said injection valves, after a certain period of operation it can be established that some of the combustion products are deposited on the valve head. In this context, it is known that such a deposit deposits more quickly and more quickly on the austenitic steel surface protective passive layer of chromium oxide (Cr 2 O 3) than, for example, on one Surface made of copper (Cu) or brass (CuZn). The deposit is mostly soot and especially coal.

Um diese Ablagerungen am Ventilkopf eines Einspritzventils zu minimieren oder gar zu verhindern, ist im Stand der Technik die Beschichtung des Ventilkopfes mit geeigneten Materialien bekannt.In order to minimize or even prevent these deposits on the valve head of an injection valve, coating of the valve head with suitable materials is known in the prior art.

So geht aus der DE 199 51 014 A1 ein Kraftstoffeinspritzventil hervor, welches der direkten Einspritzung eines Kraftstoffs wie beispielsweise Benzin oder Diesel in den Brennraum einer Brennkraftmaschine dient. Das Kraftstoffeinspritzventil weist hierfür einen Ventilkopf auf, welcher wenigstens eine Austrittsöffnung für den Kraftstoff besitzt. Ziel ist der Erhalt der Sprayparameter der Austrittsöffnung, welche durch etwaige Ablagerungen negativ verändert werden können. Um den Ventilkopf vor einer Verkokung durch Kraftstoffablagerungen sowie der Anlagerung von Rußpartikeln zu schützen, wird daher dessen Beschichtung aufgezeigt.So goes out of the DE 199 51 014 A1 a fuel injection valve, which serves the direct injection of a fuel such as gasoline or diesel in the combustion chamber of an internal combustion engine. For this purpose, the fuel injection valve has a valve head which has at least one outlet opening for the fuel. The aim is to maintain the spray parameters of the outlet, which can be negatively affected by any deposits. In order to protect the valve head from coking by fuel deposits and the deposition of soot particles, therefore, the coating is shown.

Die zur Ausbildung der Beschichtung vorgeschlagenen Materialien werden je nach den zu erreichenden Eigenschaften in drei Gruppen eingeteilt. Eine erste Gruppe von Kobalt- oder Nickeloxiden sowie Oxiden von Legierungen der genannten Metalle soll eine katalytische Umwandlung (Verbrennung) bereits abgelagerter Rußpartikel und die Ablagerung von Kohlenstoffteilchen verhindern. Zu dieser ersten Gruppe werden auch Edelmetalle wie Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Osmium (Os), Iridium (Ir) und Platin (Pt) sowie Legierungen dieser Metalle untereinander oder mit anderen Metallen gezählt. Eine zweite Gruppe an Metallen soll das Benetzungsverhalten auf der Oberfläche des Ventilkopfes derart verändern, dass die Kraftstofftröpchen abperlen und von der umgebenden Strömung mitgerissen werden können. Zu besagter zweiter Gruppe werden Keramikschichten, metallhaltige oder metallfreie Kohlenstoffschichten sowie fluorhaltige Schichten oder Saphirschichten gezählt. Die dritte und letzte Gruppe wird in der Verwendung von Nitritschichten wie beispielsweise Titannitrid (TiN) oder Chromnitrid (CrN) sowie in Oxidschichten wie beispielsweise aus Tantal- (TaO) oder Titanoxid (TiO) gesehen. Durch deren Verwendung soll eine Reaktionsschicht auf dem Ventilkopf verhindert werden.The materials proposed to form the coating are classified into three groups depending on the properties to be achieved. A first group of cobalt or nickel oxides as well as oxides of alloys of said metals is said to prevent catalytic conversion (combustion) of already deposited soot particles and deposition of carbon particles. Precious metals such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt) as well as alloys of these metals among themselves or with other metals are also included in this first group. A second group of metals is intended to alter the wetting behavior on the surface of the valve head so that the fuel droplets can bead off and be entrained by the surrounding flow. To the said second group ceramic layers, metal-containing or metal-free carbon layers and fluorine-containing layers or sapphire layers are counted. The third and last group is seen in the use of nitride layers such as titanium nitride (TiN) or chromium nitride (CrN) as well as in oxide layers such as tantalum (TaO) or titanium oxide (TiO). Their use is intended to prevent a reaction layer on the valve head.

Die DE 42 22 137 B4 ist ebenfalls auf eine Kraftstoffeinspritzdüse gerichtet, welche in Diesel-Brennkraftmaschinen einsetzbar ist. Die Kraftstoffeinspritzdüse weist einen Düsenkopf mit wenigstens einem Spritzloch auf. Um einen über konventionelle Herstellungsverfahren mittels Span abhebenden Werkzeugen nicht realisierbaren Querschnittsverlauf des Spritzlochs zu erreichen, ist eine in das Spritzloch hinein reichende Beschichtung vorgesehen. Hierdurch wird eine Modifikation und/oder Reduktion des effektiven Querschnitts des Spritzlochs erreicht, welcher sich zur Auslaufseite hin kegelstumpfförmig verengt. Zur Realisierung der Beschichtung wird die Verwendung eines Hartstoffs wie beispielsweise Chrom (Cr), Nickel (Ni), Nickel-Phosphor, Nickel-Bor oder Nickel-Kobalt-Bor sowie Aluminiumoxid (Al2O3), Chromoxid (Cr2O3), Titanoxid (TiO2), Chromkarbid (Cr3C2), Siliziumdioxid (SiO2), (AlSi), (NiCr), (WTi) oder (WC) vorgeschlagen.The DE 42 22 137 B4 is also directed to a fuel injector which is applicable to diesel engines. The fuel injector has a Nozzle head with at least one spray hole. In order to achieve a cross-sectional profile of the injection hole which can not be realized by means of cutting tools using conventional production methods, a coating extending into the injection hole is provided. As a result, a modification and / or reduction of the effective cross section of the injection hole is achieved, which narrows frustoconically to the outlet side. For the realization of the coating is the use of a hard material such as chromium (Cr), nickel (Ni), nickel-phosphorus, nickel-boron or nickel-cobalt-boron and aluminum oxide (Al 2 O 3 ), chromium oxide (Cr 2 O 3 ) , Titanium oxide (TiO 2 ), chromium carbide (Cr 3 C 2 ), silicon dioxide (SiO 2 ), (AlSi), (NiCr), (WTi) or (WC).

Gemäß der JP 2007-309167 A wird zur Vermeidung von Ablagerungen auf einem Injektor für eine Brennkraftmaschine dessen Oberflächenbeschichtung rund um ein Einspritzloch vorgeschlagen. Als Werkstoff für die Beschichtung wird Titanoxid (TiO) vorgeschlagen, um eine photokatalytische Schicht auszubilden.According to the JP 2007-309167 A For example, in order to prevent deposits on an injector for an internal combustion engine, its surface coating around an injection hole is proposed. As a material for the coating, titanium oxide (TiO) is proposed to form a photocatalytic layer.

Die JP 2005-155618 A offenbart ein Verfahren zur gleichmäßigen Ausbildung einer Schicht aus Titanoxid (TiO) in einer Einspritzdüse eines Einspritzventils für eine Brennkraftmaschine. Die besagte Schicht ist dafür vorgesehen, eine etwaige Anreicherung von Kohlenstoff-Ablagerungen zu verhindern oder zumindest zu reduzieren. Hierzu wird vorgeschlagen, zunächst wenigstens einen Abschnitt der Einspritzdüse in eine Film bildende unverdünnte Lösung mit Titan Ammoniumfluorid (NH4)2 TiF6 und Borsäure H3BO3 einzutauchen. Anschließend wird Titanoxid (TiO) auf die Oberfläche eines Ventilsitzes und der Innenseite der Einspritzdüse abgeschieden, um eine Titanoxid-Beschichtung auszubilden.The JP 2005-155618 A discloses a method for uniformly forming a layer of titanium oxide (TiO) in an injector of an injector for an internal combustion engine. Said layer is intended to prevent or at least reduce any accumulation of carbon deposits. For this purpose, it is proposed first to immerse at least one section of the injection nozzle in a film-forming undiluted solution with titanium ammonium fluoride (NH 4 ) 2 TiF 6 and boric acid H 3 BO 3 . Subsequently, titanium oxide (TiO 2) is deposited on the surface of a valve seat and the inside of the injection nozzle to form a titanium oxide coating.

Gemäß der aufgezeigten Lehren soll somit die Anreicherung von Ablagerungen an den Ventilköpfen von Einspritzventilen im Wesentlichen aus dem Grund reduziert werden, um die baulichen Sprayeigenschaften der Austrittsöffnungen möglichst lange beizubehalten. Hierbei wurde allerdings bisher nicht die sich zusätzlich aus den Ablagerungen ergebenden Nachteile in Bezug auf die Emissionen beachtet. So wird besagter Belag mit zunehmender Betriebszeit dicker, wodurch die Emissionen an flüchtigen organischen Substanzen (HC-Emissionen) zunehmen. Ursächlich hierfür sind unkontrollierte Verbrennungen etwaiger Reste an Kraftstoff. Diese werden in unerwünschter Weise über das Einspritzventil entzündet, dessen mit dem Belag behafteter Ventilkopf am Ende eines Verbrennungszyklus noch nachglimmt; vergleichbar mit einer Glühkerze.According to the teachings shown, the accumulation of deposits on the valve heads of injection valves should therefore be reduced essentially for the reason that the structural spray properties of the outlet openings should be maintained as long as possible. However, this has not hitherto taken into account the additional emissions-related disadvantages resulting from the deposits. Thus, said coating becomes thicker with increasing operating time, whereby the emissions of volatile organic substances (HC emissions) increase. This is due to uncontrolled burns of any residues of fuel. These are ignited in an undesirable manner via the injection valve, whose with the Covered valve head still smoldering at the end of a combustion cycle; comparable to a glow plug.

Auch wenn durch die im Stand der Technik vorgeschlagenen Beschichtungen bereits eine Reduzierung von Ablagerungen erreichbar ist, bietet die Ausgestaltung der in Rede stehenden Einspritzventile insbesondere in Bezug auf die durch unkontrollierte Verbrennungen entstehenden Emissionen daher noch Raum für Verbesserungen.Even if a reduction of deposits is already achievable by the coatings proposed in the prior art, the design of the injection valves in question therefore still offers room for improvement, in particular with regard to the emissions resulting from uncontrolled combustion.

Vor diesem Hintergrund liegt der Erfindung die Aufgabe zugrunde, ein Einspritzventil für eine Brennkraftmaschine, insbesondere für eine Brennkraftmaschine eines Kraftfahrzeugs dahingehend zu verbessern, dass die während des Verbrennungsvorgangs von Kraftstoff entstehenden Emissionen mit Blick auf die flüchtigen organischen Substanzen (HC-Emissionen) dauerhaft reduziert sind. Weiterhin soll ein Verfahren zur Herstellung eines Einspritzventils aufgezeigt werden, durch welches ein Einspritzventil mit im Betrieb dauerhaft reduzierten Emissionen, insbesondere solche mit flüchtigen organischen Substanzen (HC-Emissionen) gefertigt werden kann.Against this background, the object of the invention is to improve an injection valve for an internal combustion engine, in particular for an internal combustion engine of a motor vehicle, in such a way that the emissions of fuel during the combustion process are permanently reduced in view of the volatile organic substances (HC emissions) , Furthermore, a method for producing an injection valve is to be shown, by which an injection valve with permanently reduced emissions during operation, in particular those with volatile organic substances (HC emissions) can be made.

Der gegenständliche Teil dieser Aufgabe wird durch ein Einspritzventil mit den Merkmalen des Anspruchs 1 gelöst. Der verfahrensmäßige Teil der Aufgabe findet seine Lösung in den Maßnahmen des Anspruchs 6. Weitere, besonders vorteilhafte Ausgestaltungen der Erfindung offenbaren die jeweiligen Unteransprüche.The objective part of this object is achieved by an injection valve having the features of claim 1. The procedural part of the problem finds its solution in the measures of claim 6. Further, particularly advantageous embodiments of the invention disclose the respective subclaims.

Es ist darauf hinzuweisen, dass die in der nachfolgenden Beschreibung einzeln aufgeführten Merkmale sowie Maßnahmen in beliebiger, technisch sinnvoller Weise miteinander kombiniert werden können und weitere Ausgestaltungen der Erfindung aufzeigen. Die Beschreibung charakterisiert und spezifiziert die Erfindung insbesondere im Zusammenhang mit den Figuren zusätzlich.It should be noted that the features listed in the following description as well as measures in any technically meaningful way can be combined with each other and show other embodiments of the invention. The description additionally characterizes and specifies the invention, in particular in connection with the figures.

Gemäß der Erfindung wird ein Einspritzventil für eine Brennkraftmaschine aufgezeigt. Dabei kann es sich bevorzugt um eine Brennkraftmaschine eines Kraftfahrzeugs handeln. Das Einspritzventil umfasst in üblicher Weise einen Ventilkörper mit einem Ventilkopf. Der Ventilkopf ist für das Einspritzen von Kraftstoff in den Brennraum der Brennkraftmaschine vorgesehen. Aus diesem Grund ist der Ventilkopf so ausgebildet, dass dieser im eingebauten Zustand des Einspritzventils in der Brennkraftmaschine zumindest abschnittsweise in dem Brennraum angeordnet ist. Sofern der Ventilkopf möglichst bündig mit jenen, den Brennraum begrenzenden Flächen ausgebildet sein soll, ist der Ventilkopf dem Brennraum zumindest unmittelbar zugewandt. Weiterhin ist besagter Ventilkopf wenigstens bereichsweise mit einer ersten Oxid-Schicht beschichtet.According to the invention, an injection valve for an internal combustion engine is shown. This may preferably be an internal combustion engine of a motor vehicle. The injection valve conventionally comprises a valve body with a valve head. The valve head is provided for the injection of fuel into the combustion chamber of the internal combustion engine. For this reason, the valve head is designed so that this in the installed state of the injection valve in the Internal combustion engine is at least partially disposed in the combustion chamber. If the valve head as flush as possible with those, the combustion chamber bounding surfaces to be formed, the valve head is at least directly facing the combustion chamber. Furthermore, said valve head is at least partially coated with a first oxide layer.

Erfindungsgemäß ist über der ersten Oxid-Schicht eine katalytische zweite Oxid-Schicht aus Ceroxid (CeO2) angeordnet. Alternativ hierzu kann die zweite Oxid-Schicht auch aus Praseodymoxid (PrO2) oder Zirconiumoxid (ZrO2) bestehen. In einer weiteren alternativen Ausgestaltung kann sich die zweite Oxid-Schicht auch aus Ceroxid (CeO2) und Praseodymoxid (PrO2) oder aus Ceroxid (CeO2) und Zirconiumoxid (ZrO2) zusammensetzen. Überdies ist auch eine Zusammensetzung der zweiten Oxid-Schicht aus Praseodymoxid (PrO2) und Zirconiumoxid (ZrO2) denkbar.According to the invention, a catalytic second oxide layer of cerium oxide (CeO 2 ) is arranged above the first oxide layer. Alternatively, the second oxide layer may also consist of praseodymium oxide (PrO 2 ) or zirconium oxide (ZrO 2 ). In a further alternative embodiment, the second oxide layer may also be composed of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) or cerium oxide (CeO 2) and zirconia (ZrO 2). Moreover, a composition of the second oxide layer of praseodymium oxide (PrO 2 ) and zirconium oxide (ZrO 2 ) is also conceivable.

Der besondere Vorteil der jeweils allein oder in einer Kombination miteinander auftretenden Oxid-Verbindungen beruht auf deren guten Eigenschaften zur Speicherung von Sauerstoff (O2). So bewirken diese Verbindungen jeweils für sich genommen oder aber in einer jeweiligen Konstellation miteinander eine Reduzierung der Anspringtemperatur des Kraftstoffs sowie von unverbranntem Kohlenwasserstoff (CH) und Kohlenstoffmonoxid (CO), wodurch sich die Emissionen der im Betrieb befindlichen Brennkraftmaschine herabsetzen lassen.The particular advantage of each occurring alone or in combination with each other oxide compounds based on their good properties for the storage of oxygen (O 2 ). Thus, these compounds, taken alone or in a particular constellation with each other to reduce the light-off temperature of the fuel and unburned hydrocarbon (CH) and carbon monoxide (CO), which can reduce the emissions of the internal combustion engine in operation.

Eine vorteilhafte Weiterbildung des grundsätzlichen Erfindungsgedankens sieht vor, dass die erste Oxid-Schicht aus Titanoxid (TiO2) gebildet sein kann. Alternativ hierzu kann die erste Oxid-Schicht auch aus Aluminiumoxid (Al2O3) bestehen. Bei der jeweiligen Oxid-Verbindung aus Titan (Ti) und/oder porösen keramischen Oxid-Schicht aus Aluminium (Al) handelt es sich um ideale Träger für die zweite katalytische Oxid-Schicht. Bevorzugt weist die erste Oxid-Schicht dabei eine Dicke von 10,0 bis 20,0 µm auf.An advantageous development of the basic concept of the invention provides that the first oxide layer can be formed from titanium oxide (TiO 2 ). Alternatively, the first oxide layer may also consist of aluminum oxide (Al 2 O 3 ). The respective oxide compound of titanium (Ti) and / or porous ceramic oxide layer of aluminum (Al) are ideal supports for the second catalytic oxide layer. In this case, the first oxide layer preferably has a thickness of 10.0 to 20.0 μm.

Insbesondere Aluminiumoxid (Al2O3) zeichnet sich aufgrund seiner hohen Temperaturbeständigkeit, seiner großen Oberfläche sowie seiner vorteilhaften Säure-Basen-Eigenschaften und durch seine gute Wechselwirkung mit anderen Metallen als Trägermaterial für Katalysatoren aus.In particular, aluminum oxide (Al 2 O 3 ) is characterized by its high temperature resistance, its high surface area and its advantageous acid-base properties and by its good interaction with other metals as a support material for catalysts.

Im Rahmen der Erfindung wird es als vorteilhaft angesehen, wenn die erste Oxid-Schicht mit Kupferoxid (CuO) imprägniert ist. Alternativ hierzu kann auch die zweite Oxid-Schicht mit Kupferoxid imprägniert sein. Selbstverständlich können ebenso sowohl die erste Oxid-Schicht als auch die zweite Oxid-Schicht mit Kupferoxid (CuO) imprägniert sein. Der Vorteil aus der Imprägnierung mit Kupferoxid (CuO) besteht in einer Beseitigung oder aber Verminderung bis hin zur Verhinderung von Anlagerungen auf dem so beschichteten Ventilkopf. Hierbei steht die Verbrennung von Ruß im Vordergrund. Ursächlich hierfür ist insbesondere der so aus Ceroxid (CeO2) und Kupferoxid (CuO) oder Praseodymoxid (PrO2) und Kupferoxid (CuO) bestehende und auf dem Ventilkopf abgeschiedene Katalysator aus diesen Verbindungen. Durch besagte Imprägnierung wird eine weitere Reduzierung der Anspringtemperatur brennbarer Bestandteile ermöglicht.In the context of the invention, it is considered advantageous if the first oxide layer is impregnated with copper oxide (CuO). Alternatively, the second oxide layer may be impregnated with copper oxide. Of course, both the first oxide layer and the second oxide layer may be impregnated with copper oxide (CuO) as well. The advantage of impregnation with copper oxide (CuO) is the elimination or reduction, up to the prevention of deposits on the thus coated valve head. Here, the combustion of soot in the foreground. This is due in particular to the catalyst consisting of cerium oxide (CeO 2 ) and copper oxide (CuO) or praseodymium oxide (PrO 2 ) and copper oxide (CuO) and deposited on the valve head from these compounds. Said impregnation enables a further reduction of the light-off temperature of combustible constituents.

Im Zusammenhang mit den sich aus einer Imprägnierung der ersten und/oder zweiten Oxid-Schicht ergebenden Vorteilen ist vorgesehen, dass die erste Oxid-Schicht und/oder die zweite Oxid-Schicht mit Platin (Pt) und/oder einem weiteren Element aus der Gruppe von Platinmetallen imprägniert sein können/kann. Bei den Platinmetallen handelt es sich neben Platin (Pt) insbesondere um Ruthenium (Ru) und/oder Osmium (Os) und/oder Rhodium (Rh) und/oder Iridium (Ir) und/oder Palladium (Pd). Der sich aus der Imprägnierung mit einem oder mehreren der zuvor genannten Elemente ergebende Vorteil besteht ebenfalls in einer Beseitigung oder aber Verminderung bis hin zur Verhinderung von Anlagerungen auf dem so beschichteten Ventilkopf. So ist durch besagte Imprägnierung weiterhin eine Reduzierung der Anspringtemperatur brennbarer Bestandteile erreichbar.In connection with the advantages resulting from an impregnation of the first and / or second oxide layer, provision is made for the first oxide layer and / or the second oxide layer to be provided with platinum (Pt) and / or another element from the group may be impregnated by platinum metals. The platinum metals are in addition to platinum (Pt) in particular ruthenium (Ru) and / or osmium (Os) and / or rhodium (Rh) and / or iridium (Ir) and / or palladium (Pd). The advantage resulting from the impregnation with one or more of the aforementioned elements is also an elimination or reduction, up to the prevention of deposits on the thus coated valve head. Thus, by means of said impregnation, a further reduction in the light-off temperature of combustible constituents can be achieved.

Als besonders vorteilhafte Ausgestaltung wird vorgeschlagen, dass wenigstens der Ventilkopf des Einspritzventils zumindest teilweise aus einem pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) gebildet ist. Bei dem Al-Si-Werkstoffs des Herstellers PEAK handelt es sich um einen Aluminiumwerkstoff AlSi20Fe5Ni2, welcher gegenüber konventionellen Aluminiumlegierungen eine überaus hohe Festigkeit und Steifigkeit besitzt. Neben dem ohnehin schon geringen Gewicht des Aluminiumwerkstoffs sind so Zugfestigkeiten bis zu 750 N/mm2 erreichbar. Insbesondere der hohe Anteil an primär ausgeschiedenem Silizium bewirkt eine naturharte Oberfläche. Die auf der Oberfläche ausgeschiedenen Silizium-Partikel bilden eine gleichmäßige Schichtdicke von 4,0 bis 5,0 µm. Hierdurch weist der zumindest teilweise aus S250 gefertigte Ventilkopf bereits ohne eine Beschichtung eine hohe Verschleißfestigkeit auf. Hinzu kommen die hohe Hitzebeständigkeit und insbesondere die gute Zerspanbarkeit. So können die erforderlichen Austrittsöffnungen ohne die Notwendigkeit eines Entgratens in den so gebildeten Ventilkopf eingebracht werden. Der als Ventilkopf verwendete Aluminiumwerkstoff AlSi20Fe5Ni2 dient als Substrat für die Beschichtung mit den erfindungsgemäßen Elementen und/oder Verbindungen.As a particularly advantageous embodiment, it is proposed that at least the valve head of the injection valve is formed at least partially from a powder metallurgical Al-Si material (PEAK S250). The Al-Si material of the manufacturer PEAK is an aluminum material AlSi 20 Fe 5 Ni 2 , which has a very high strength and rigidity compared to conventional aluminum alloys. In addition to the already low weight of the aluminum material, tensile strengths of up to 750 N / mm 2 can be achieved. In particular, the high proportion of primarily precipitated silicon causes a natural surface. The precipitated on the surface silicon particles form a uniform layer thickness from 4.0 to 5.0 μm. As a result, the valve head produced at least partially from S250 already has a high wear resistance without a coating. In addition there are the high heat resistance and especially the good machinability. Thus, the required outlet openings can be introduced into the valve head thus formed without the need for deburring. The aluminum material AlSi 20 Fe 5 Ni 2 used as valve head serves as substrate for the coating with the elements and / or compounds according to the invention.

Alternativ zu der Verwendung des pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) kann der Ventilkopf zumindest teilweise aus einer Titanlegierung (Ti6Al4V) gebildet sein. Im Vergleich zu der Verwendung des Al-Si-Werkstoffs weist die Titanlegierung eine schwierigere Bearbeitbarkeit auf, insbesondere beim Einbringen der erforderlichen Austrittsöffnungen. Weiterhin wurde im Rahmen von Versuchen festgestellt, dass die zweite Oxid-Schicht aus Ceroxid (CeO2) auf der Titanlegierung weniger effektiv ist als auf dem erfindungsgemäßen Al-Si-Werkstoff.As an alternative to the use of the powder metallurgical Al-Si material (PEAK S250), the valve head can be formed at least partially from a titanium alloy (Ti6Al4V). Compared to the use of the Al-Si material, the titanium alloy has a more difficult workability, especially when introducing the required outlet openings. Furthermore, it has been found in experiments that the second oxide layer of cerium oxide (CeO 2 ) on the titanium alloy is less effective than on the Al-Si material according to the invention.

Die vorliegende Erfindung zeigt ein gegenüber dem Stand der Technik verbessertes Einspritzventil im Bereich seines Ventilkopfes. So verhindert insbesondere die erfindungsgemäße Oberfläche des Ventilkopfes eine Ablagerung flüssigen Kraftstoffs in Form von Tröpchen, welche ansonsten auf der Oberfläche des Ventilkopfes eintrocknen. Hier hinterlassen sie nach einiger Zeit Teer- und/oder Kohle-Beläge, die nicht ohne weiteres zu entfernen sind. Derartige Beläge haben einen negativen Effekt auf die Emissionen der im Betrieb befindlichen Brennkraftmaschine. Insbesondere die Wirkung der erfindungsgemäßen Beschichtung des Ventilkopfes als Katalysator bewirkt, dass die besagten Tröpchen auf der Oberfläche des Ventilkopfes verdampfen und so keine Beläge bilden können.The present invention shows an improved over the prior art injection valve in the region of its valve head. In particular, the inventive surface of the valve head prevents deposition of liquid fuel in the form of droplets, which otherwise dry on the surface of the valve head. Here they leave after some time tar and / or coal deposits, which are not easy to remove. Such pads have a negative effect on the emissions of the internal combustion engine in operation. In particular, the effect of the inventive coating of the valve head as a catalyst causes the said droplets to evaporate on the surface of the valve head and thus can not form deposits.

Weiterhin wird im Rahmen der Erfindung ein Verfahren aufgezeigt, mit welchem sich ein zuvor aufgezeigtes verbessertes Einspritzventil für eine Brennkraftmaschine, insbesondere für eine Brennkraftmaschine eines Kraftfahrzeugs herstellen lässt. Besagtes Einspritzventil umfasst einen Ventil körper mit einem Ventilkopf. Der Ventilkopf ist dazu ausgebildet, um im eingebauten Zustand des Einspritzventils in der Brennkraftmaschine zumindest abschnittsweise in einem Brennraum der Brennkraftmaschine angeordnet oder diesem zumindest unmittelbar zugewandt zu sein. Der Ventilkopf wird wenigstens bereichsweise mit einer ersten Oxid-Schicht beschichtet.Furthermore, in the context of the invention, a method is shown with which a previously shown improved injection valve for an internal combustion engine, in particular for an internal combustion engine of a motor vehicle can be produced. Said injection valve comprises a valve body with a valve head. The valve head is designed to be arranged in the internal combustion engine at least in sections in a combustion chamber of the internal combustion engine in the installed state of the injection valve, or at least partially facing it be. The valve head is at least partially coated with a first oxide layer.

Erfindungsgemäß wird über der ersten Oxid-Schicht eine zweite Oxid-Schicht als Washcoat aufgebracht. Dabei besteht die erfindungsgemäße als Washcoat aufgebrachte zweite Oxid-Schicht aus Ceroxid (CeO2). Alternativ hierzu kann die zweite Oxid-Schicht auch aus Praseodymoxid (PrO2) oder Zirconiumoxid (ZrO2) bestehen. In einer weiteren alternativen Ausgestaltung kann sich die als Washcoat aufgebrachte zweite Oxid-Schicht auch aus Ceroxid (CeO2) und Praseodymoxid (PrO2) oder aus Ceroxid (CeO2) und Zirconiumoxid (ZrO2) zusammensetzen. Überdies ist auch eine Zusammensetzung der zweiten Oxid-Schicht aus Praseodymoxid (PrO2) und Zirconiumoxid (ZrO2) denkbar.According to the invention, a second oxide layer is applied as a washcoat over the first oxide layer. The second oxide layer according to the invention applied as washcoat consists of cerium oxide (CeO 2 ). Alternatively, the second oxide layer may also consist of praseodymium oxide (PrO 2 ) or zirconium oxide (ZrO 2 ). In a further alternative embodiment, the applied as a washcoat second oxide layer may also be composed of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) or cerium oxide (CeO 2) and zirconia (ZrO 2). Moreover, a composition of the second oxide layer of praseodymium oxide (PrO 2 ) and zirconium oxide (ZrO 2 ) is also conceivable.

Die sich aus der Verwendung der vorgenannten Verbindungen und den nachfolgend beschriebenen Maßnahmen ergebenden Vorteile wurden bereits zuvor im Zusammenhang mit dem erfindungsgemäßen Einspritzventil erläutert und gelten für das erfindungsgemäße Verfahren zur Herstellung eines solchen Einspritzventils entsprechend.The advantages resulting from the use of the abovementioned compounds and the measures described below have already been explained above in connection with the injection valve according to the invention and apply correspondingly to the method according to the invention for producing such an injection valve.

Um eine oder mehrere der erfindungsgemäßen Verbindungen in Form einer zweiten Oxid-Schicht als Washcoat auf die erste Oxid-Schicht des Ventilkopfes aufzubringen, liegt diese zunächst als Pulversuspension vor. Diese Pulversuspension wird anschließend beispielsweise als wässrige Suspension auf das Substrat in Form des bereits mit der ersten Oxid-Schicht beschichteten Ventilkopfes aufgebracht und angetrocknet. Durch eine anschließende Kalzinierung wird die so aufgebrachte Suspension aktiviert.In order to apply one or more of the compounds according to the invention in the form of a second oxide layer as a washcoat to the first oxide layer of the valve head, this is initially present as a powder suspension. This powder suspension is then applied, for example, as an aqueous suspension to the substrate in the form of the already coated with the first oxide layer valve head and dried. By subsequent calcination, the suspension thus applied is activated.

In einer Weiterführung des erfindungsgemäßen Verfahrens ist vorgesehen, dass die erste Oxid-Schicht aus Titanoxid (TiO2) gebildet wird. Alternativ hierzu kann die erste Oxid-Schicht auch aus Aluminiumoxid (Al2O3) gebildet werden. Bevorzugt wird die erste Oxid-Schicht dabei mit einer Dicke von 10,0 bis 20,0 µm zumindest bereichsweise auf die Oberfläche des Ventilkopfes aufgebracht.In a continuation of the method according to the invention, it is provided that the first oxide layer is formed from titanium oxide (TiO 2 ). Alternatively, the first oxide layer may be formed of alumina (Al 2 O 3 ). In this case, the first oxide layer is preferably applied to the surface of the valve head at least in regions with a thickness of 10.0 to 20.0 μm.

Erfindungsgemäß kann die erste Oxid-Schicht mittels einer Micro Arc Oxidation (MAO) auf den Ventilkopf aufgebracht werden. Alternativ hierzu kann die erste Oxid-Schicht auch durch eine Plasmaelektrolytische Oxidation (PEO) auf den Ventilkopf aufgebracht werden. Durch die Micro Arc Oxidation werden die Eigenschaften der Oberfläche des Ventilkopfes insofern verbessert, dass diese unter anderem an Härte und Verschleißfestigkeit zunimmt. Selbiges gilt für die Plasmaelektrolytische Oxidation (PEO), bei welcher die Oberfläche des Ventilkopfes in einer Plasmaentladung umgewandelt wird. Durch die genannten Verfahren wird die erste Oxid-Schicht in vorteilhafter Weise in eine dichte, atomar haftende Keramikschicht umgewandelt.According to the invention, the first oxide layer can be applied to the valve head by means of a micro arc oxidation (MAO). Alternatively, the first Oxide layer can also be applied by a plasma electrolytic oxidation (PEO) on the valve head. The Micro Arc Oxidation improves the surface properties of the valve head, increasing its hardness and wear resistance, among other things. The same applies to the plasma electrolytic oxidation (PEO), in which the surface of the valve head is converted into a plasma discharge. By the mentioned method, the first oxide layer is advantageously converted into a dense, atomically adhering ceramic layer.

Im Rahmen der Erfindung wird es als vorteilhaft angesehen, wenn die erste Oxid-Schicht mit Kupferoxid (CuO) imprägniert wird. Alternativ hierzu kann auch die zweite Oxid-Schicht mit Kupferoxid imprägniert werden. Selbstverständlich können ebenso sowohl die erste Oxid-Schicht als auch die zweite Oxid-Schicht mit Kupferoxid (CuO) imprägniert werden.In the context of the invention, it is considered advantageous if the first oxide layer is impregnated with copper oxide (CuO). Alternatively, the second oxide layer can be impregnated with copper oxide. Of course, both the first oxide layer and the second oxide layer may be impregnated with copper oxide (CuO) as well.

Im Zusammenhang mit den sich aus einer Imprägnierung der ersten und/oder zweiten Oxid-Schicht ergebenden Vorteilen ist vorgesehen, dass die erste Oxid-Schicht und/oder die zweite Oxid-Schicht mit Platin (Pt) und/oder einem weiteren Element aus der Gruppe von Platinmetallen imprägniert werden können/kann. Bei den Platinmetallen handelt es sich neben Platin (Pt) insbesondere um Ruthenium (Ru) und/oder Osmium (Os) und/oder Rhodium (Rh) und/oder Iridium (Ir) und/oder Palladium (Pd).In connection with the advantages resulting from an impregnation of the first and / or second oxide layer, provision is made for the first oxide layer and / or the second oxide layer to be provided with platinum (Pt) and / or another element from the group of platinum metals can / can be impregnated. The platinum metals are in addition to platinum (Pt) in particular ruthenium (Ru) and / or osmium (Os) and / or rhodium (Rh) and / or iridium (Ir) and / or palladium (Pd).

Als besonders vorteilhafte Ausgestaltung wird vorgeschlagen, dass wenigstens der Ventilkopf des Einspritzventils zumindest teilweise aus einem pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) gebildet wird. Als geeignetes Verfahren zu dessen Herstellung wird z. B. das Osprey-Verfahren zum Sprühkompaktieren vorgeschlagen. Hierbei kann die Schmelze des Al-Si-Werkstoffs über eine Düse auf eine gekühlte Kupferplatte aufgebracht werden. Die so gebildeten sprühkompaktierten Bolzen werden anschließend durch Extrudieren zu Stangen oder Rohren weiterverarbeitet.As a particularly advantageous embodiment, it is proposed that at least the valve head of the injection valve is formed at least partially from a powder metallurgical Al-Si material (PEAK S250). As a suitable method for its production z. B. proposed the Osprey method for spray compacting. In this case, the melt of the Al-Si material can be applied via a nozzle to a cooled copper plate. The spray-compacted bolts thus formed are then further processed by extrusion into rods or tubes.

Alternativ kann auch eine hochwarmfeste Aluminium, z.B. PLM908 von Powder-Light-Metals verwendet werden. Hierbei ergeben sich noch höhere Warmzugfestigkeiten aufgrund der weiter erhöhten Abkühlungsgeschwindigkeit, wobei flüssige Aluminium-Tröpfchen auf ein schnell rotierendes, gekühltes Kupferrad gegossen werden. Die so entstandenen Aluminium-Bänder werden anschließend kompaktiert und zur Herstellung von Halbzeug extrudiert. Über die schnelle Rotation des Kupferrades wird die Schmelze derart schnell abgekühlt, dass diese sofort erstarrt. Aufgrund der hohen Rotationsgeschwindigkeit des Kupferrades wird der so erzeugte Strang anschließend abgeschleudert. Der Vorteil dieses Verfahrens besteht in dem Erhalt einer bevorzugten Gefügestruktur des so erzeugbaren Ventilkopfes.Alternatively, a high-temperature aluminum, eg PLM908 Powder Light Metals can be used. This results in even higher hot tensile strength due to the further increased cooling rate, with liquid aluminum droplets on a rapidly rotating, cooled copper wheel to be poured. The resulting aluminum strips are then compacted and extruded to produce semi-finished products. The rapid rotation of the copper wheel cools the melt down so quickly that it solidifies immediately. Due to the high rotational speed of the copper wheel of the strand thus produced is then thrown off. The advantage of this method consists in obtaining a preferred microstructure of the valve head which can be produced in this way.

Bei dem Al-Si-Werkstoffs des Herstellers PEAK handelt es sich um einen Aluminiumwerkstoff AlSi20Fe5Ni2, welcher gegenüber konventionellen Aluminiumlegierungen eine überaus hohe Festigkeit und Steifigkeit besitzt.The Al-Si material of the manufacturer PEAK is an aluminum material AlSi 20 Fe 5 Ni 2 , which has a very high strength and rigidity compared to conventional aluminum alloys.

Alternativ zu der Verwendung des pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) kann der Ventilkopf zumindest teilweise aus einer Titanlegierung (Ti6Al4V) gebildet werden. Als geeignetes Verfahren zu dessen Herstellung wird auch hierfür das zuvor erläuterte Schmelzschleudern vorgeschlagen.As an alternative to the use of the powder metallurgical Al-Si material (PEAK S250), the valve head can be formed at least partially from a titanium alloy (Ti6Al4V). As a suitable method for its production, the above-described melt spinning is also proposed for this purpose.

Weitere vorteilhafte Einzelheiten und Wirkungen der Erfindung sind im Folgenden anhand von unterschiedlichen, in den Figuren dargestellten Ausführungsbeispielen näher erläutert. Es zeigen:

Fig. 1
eine schematische Darstellung eines erfindungsgemäßen Einspritzventils in einer Seitenansicht,
Fig. 2
das Einspritzventil aus Fig. 1 mit Blick auf dessen endseitigen Ventilkopf sowie
Fig. 3
ein Diagramm mit der Aufzeichnung des Gewichts an Ruß in Bezug auf dessen unterschiedliche Oxidationstemperaturen an einem unbeschichteten und an einem erfindungsgemäß beschichteten Ventilkopf eines Einspritzventils aus den Fig. 1 und 2.
Further advantageous details and effects of the invention are explained in more detail below with reference to exemplary embodiments illustrated in the figures. Show it:
Fig. 1
a schematic representation of an injection valve according to the invention in a side view,
Fig. 2
the injection valve off Fig. 1 with a view of its end valve head as well
Fig. 3
a diagram with the recording of the weight of soot with respect to its different oxidation temperatures on an uncoated and coated according to the invention a valve head of an injection valve of the Fig. 1 and 2 ,

Fig. 1 ist eine schematische Darstellung eines erfindungsgemäßen Einspritzventils 1 zu entnehmen. Besagtes Einspritzventil 1 ist für die Verwendung in einer nicht näher dargestellten Brennkraftmaschine vorgesehen. Bei der Brennkraftmaschine kann es sich insbesondere um eine Brennkraftmaschine eines Kraftfahrzeugs handeln. Fig. 1 is a schematic representation of an injection valve 1 according to the invention can be seen. Said injection valve 1 is intended for use in an internal combustion engine, not shown. The internal combustion engine may in particular be an internal combustion engine of a motor vehicle.

Weiterhin ist ein Abschnitt einer Wandung 2 eines Zylinderkopfes 3 der nicht weiter gezeigten Brennkraftmaschine angedeutet, durch welche hindurch das Einspritzventil 1 angeordnet ist. Hierbei ragt ein Teilbereich des Einspritzventils 1 in einen Brennraum 4 der Brennkraftmaschine.Furthermore, a portion of a wall 2 of a cylinder head 3 of the internal combustion engine not shown is indicated, through which the injection valve 1 is arranged. In this case, a partial region of the injection valve 1 protrudes into a combustion chamber 4 of the internal combustion engine.

Das Einspritzventil 1 umfasst im Wesentlichen einen Ventilkörper 5. Der dem Brennraum 4 zugewandte, insbesondere zumindest teilweise in diesem angeordnete Abschnitt des Ventilkörpers 5 weist einen Ventilkopf 6 auf. Der Ventilkopf 6 ist zumindest teilweise aus einem pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) oder aus einer Titanlegierung (Ti6Al4V) gebildet. Die in eine Längsrichtung a des Einspritzventils 1 verlaufenden punktierten Linien dienen der Verdeutlichung eines Kanals 7 innerhalb des Einspritzventils 1. Durch diesen Kanal 7 hindurch ist ein nicht näher gezeigter Kraftstoff über das Einspritzventil 1 in den Brennraum 4 hinein einspritzbar.The injection valve 1 essentially comprises a valve body 5. The combustion chamber 4 facing, in particular at least partially arranged in this section of the valve body 5 has a valve head 6. The valve head 6 is formed at least partially from a powder metallurgical Al-Si material (PEAK S250) or from a titanium alloy (Ti 6 Al 4 V). The dotted lines extending in a longitudinal direction a of the injection valve 1 serve to illustrate a channel 7 within the injection valve 1. Through this channel 7, a fuel (not shown) can be injected into the combustion chamber 4 via the injection valve 1.

Vorliegend ist zumindest eine Stirnseite 8 des Ventilkopfes 6 angedeutet mit einer ersten Oxid-Schicht 9 und einer auf der ersten Oxid-Schicht 9 angeordneten zweiten Oxid-Schicht 10 versehen. Vorliegend ist die erste Oxid-Schicht 9 aus Titanoxid (TiO2) und/oder Aluminiumoxid (Al2O3) gebildet. Demgegenüber besteht die zweite Oxid-Schicht aus Ceroxid (CeO2). Alternativ hierzu kann die zweite Oxid-Schicht auch aus Praseodymoxid (PrO2) oder Zirconiumoxid (ZrO2) bestehen. In einer weiteren alternativen Ausgestaltung kann sich die als Washcoat aufgebrachte zweite Oxid-Schicht auch aus Ceroxid (CeO2) und Praseodymoxid (PrO2) oder aus Ceroxid (CeO2) und Zirconiumoxid (ZrO2) zusammensetzen. Überdies ist auch eine Zusammensetzung der zweiten Oxid-Schicht aus Praseodymoxid (PrO2) und Zirconiumoxid (ZrO2) denkbar.In the present case, at least one end face 8 of the valve head 6 is indicated with a first oxide layer 9 and a second oxide layer 10 arranged on the first oxide layer 9. In the present case, the first oxide layer 9 is formed from titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ). In contrast, the second oxide layer consists of cerium oxide (CeO 2 ). Alternatively, the second oxide layer may also consist of praseodymium oxide (PrO 2 ) or zirconium oxide (ZrO 2 ). In a further alternative embodiment, the applied as a washcoat second oxide layer may also be composed of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) or cerium oxide (CeO 2) and zirconia (ZrO 2). Moreover, a composition of the second oxide layer of praseodymium oxide (PrO 2 ) and zirconium oxide (ZrO 2 ) is also conceivable.

Weiterhin sind die erste Oxid-Schicht 9 und/oder die zweite Oxid-Schicht 10 in nicht näher gezeigter Weise mit Kupferoxid (CuO) imprägniert. Eine weitere Imprägnierung der ersten Oxid-Schicht 9 und/oder der zweite Oxid-Schicht 10 ist ferner über wenigstens ein oder mehrere ebenfalls nicht näher dargestellte Elemente aus der Gruppe der Platinmetalle gegeben. Besagte Gruppe besteht aus Ruthenium (Ru), Osmium (Os), Rhodium (Rh), Iridium (Ir), Palladium (Pd) und Platin (Pt).Furthermore, the first oxide layer 9 and / or the second oxide layer 10 are impregnated in a manner not shown in detail with copper oxide (CuO). A further impregnation of the first oxide layer 9 and / or the second oxide layer 10 is further given by at least one or more elements also not shown in detail from the group of platinum metals. Said group consists of ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd) and platinum (Pt).

Fig. 2 zeigt das Einspritzventil 1 aus Fig. 1 mit Blick auf die Stirnseite 8 des Ventilkopfes 6. Um den vorliegenden Blick in Längsrichtung a des Einspritzventils 1 möglichst übersichtlich zu gestalten, wurden etwaige Andeutungen der Wandung 2 des Zylinderkopfes 3 sowie der außerhalb des Brennraums 4 gelegene und in Fig. 1 dargestellte Endbereich des Einspritzventils 1 weggelassen. Fig. 2 shows the injection valve 1 from Fig. 1 In order to make the present view in the longitudinal direction a of the injection valve 1 as clear as possible, any hints of the wall 2 of the cylinder head 3 and the outside of the combustion chamber 4 were located and in Fig. 1 shown end portion of the injection valve 1 omitted.

Wie zu erkennen, weist der Ventilkopf 6 mehrere in dieser Ansicht von außen sichtbare Austrittsöffnungen 11 auf, aus welchen heraus in nicht näher dargestellter Weise der Kraftstoff in den Brennraum 4 eintreten kann. Die Austrittsöffnungen 11 sind mit einer Anzahl von sechs in radial gleichem Abstand zu der zentralen Längsachse a des Einspritzventils 1 um diese herum verteilt. Dabei weisen sie einen gleichbleibenden Abstand unter sich auf, so dass sie jeweils um einen gleichen Winkel b zueinander versetzt angeordnet sind.As can be seen, the valve head 6 has a plurality of outlet openings 11, visible from the outside in this view, from which the fuel can enter the combustion chamber 4 in a manner not shown in detail. The outlet openings 11 are distributed with a number of six at a radially equal distance from the central longitudinal axis a of the injection valve 1 around it. In this case, they have a constant distance below each other, so that they are each offset by an equal angle b to each other.

Fig. 3 ist ein Diagramm mit Messergebnissen eines Versuchs gezeigt. Innerhalb des Diagramms sind zwei Kurven c, d zu erkennen. Aus den beiden Kurven c, d geht ein Gewicht e von auf dem Ventilkopf 6 abgesetztem Ruß hervor, bezogen auf dessen anfängliches Ausgangsgewicht. Besagter Ruß wird über die Zeit oxidiert, so dass dessen Gewicht e abnimmt. Die Kurven c, d sind über eine Temperatur f in °C aufgetragen. Während eine mit durchgezogener Linie gezeigte erste Kurve c die Messergebnisse an einem normalen unbeschichteten Ventilkopf 6 zeigt, sind der verbleibenden, mit unterbrochener Linie gezeigten Kurve d die Messergebnisse an einem erfindungsgemäß beschichteten sowie imprägnierten Ventilkopf 6 dargestellt. Fig. 3 a diagram is shown with measurement results of an experiment. Within the diagram, two curves c, d can be seen. From the two curves c, d, a weight e of deposited on the valve head 6 soot emerges, based on its initial initial weight. Said soot is oxidized over time, so that its weight e decreases. The curves c, d are plotted against a temperature f in ° C. While a first curve c shown by a solid line shows the measurement results on a normal uncoated valve head 6, the remaining curve d shown with a broken line shows the measurement results on a valve head 6 coated and impregnated according to the invention.

Das vorliegende Diagramm dient der Darstellung der verbesserten Verbrennung von Ruß an dem mit einer katalytischen zweiten Oxid-Schicht 10 aus Ceroxid (CeO2) und Praseodymoxid (PrO2) beschichteten Ventilkopf 6. Hierfür wurde der aus dem Aluminiumwerkstoff AlSi20Fe5Ni2 gebildete Ventilkopf 6 mit der ersten Oxid-Schicht 9 und der zweiten Oxid-Schicht 10 aus Ceroxid (CeO2) und Praseodymoxid (PrO2) beschichtet sowie mit Kupferoxid (CuO) imprägniert. Bevorzug lagert sich das Kupferoxid (CuO) nur in der zweiten Oxid-Schicht 10 ab.This diagram is used to represent the improved combustion of soot on the with a catalytic second oxide layer 10 made of cerium oxide (CeO 2) and praseodymium oxide (PrO 2) coated valve head 6. For this purpose, consisting of the aluminum material AlSi 20 Fe 5 Ni 2 was formed Valve head 6 with the first oxide layer 9 and the second oxide layer 10 of cerium oxide (CeO 2 ) and praseodymium oxide (PrO 2 ) coated and impregnated with copper oxide (CuO). Preferably, the copper oxide (CuO) deposits only in the second oxide layer 10.

Bei dem in der ersten Kurve c gezeigten Ruß handelt es sich um synthetischen Ruß, welcher im Vergleich zu Diesel- und Benzin-Ruß stabiler ist und bei höheren Temperaturen verbrennt. Insofern sind die bei der Verbrennung des Rußes in der ersten Kurve c über 70 °C niedrigeren Temperaturen signifikant für die Verbrennung von Ruß am Ceroxid (CeO2) und Praseodymoxid (PrO2) enthaltenden Katalysator aus Kupferoxid (CuO).The soot shown in the first curve c is synthetic soot, which is more stable compared to diesel and gasoline soot and burns at higher temperatures. In this respect, the combustion of soot in the first curve c above 70 ° C lower temperatures significantly for the combustion of soot on ceria (CeO 2 ) and praseodymium oxide (PrO 2 ) containing catalyst of copper oxide (CuO).

Die aufgezeigten Messergebnisse in Fig. 3 entstammen Testergebnissen über die Verbrennung von synthetischem Ruß in einem Labor, welche über ein Thermogravimetrisches Analysegerät (TGA) gewonnen wurde. Der verwendete Ruß wurde von Hiden, UK aus einem Quarzrohr hergestellt. Hierfür wurden ca. 40,0 Milligramm an Ruß mit 120,0 Milligramm Siliciumkarbid (SiC) vermischt. Weiterhin wurde alternativ ein Katalysator hinzugegeben. Anschließend wurde der so präparierte Ventilkopf in den Korb des Thermogravimetrischen Analysegeräts (TGA) gegeben. Die Probe aus dem Ventilkopf wurde dabei mit 8% Sauerstoff (O2) umgeben. Anschließend erfolgte eine Erhitzung der Probe auf 800 °C mit einem Temperaturanstieg von 10 °C pro Minute. Die entstandenen Reaktionsgase wurden mit einem Massenspektrometer gemessen.The shown measurement results in Fig. 3 come from test results on the combustion of synthetic soot in a laboratory, which was obtained via a thermogravimetric analyzer (TGA). The carbon black used was made by Hiden, UK from a quartz tube. For this purpose, about 40.0 milligrams of carbon black were mixed with 120.0 milligrams of silicon carbide (SiC). Furthermore, alternatively, a catalyst was added. Subsequently, the thus prepared valve head was placed in the basket of the thermogravimetric analyzer (TGA). The sample from the valve head was surrounded by 8% oxygen (O 2 ). Subsequently, the sample was heated to 800 ° C with a temperature increase of 10 ° C per minute. The resulting reaction gases were measured by a mass spectrometer.

BezugszeichenlisteLIST OF REFERENCE NUMBERS

11
EinspritzventilInjector
22
Wandung von 3Wall of 3
33
Zylinderkopfcylinder head
44
Brennraumcombustion chamber
55
Ventilkörper von 1Valve body of 1
66
Ventilkopf von 1Valve head from 1
77
Kanal in 1Channel in 1
88th
Stirnseite von 6Front side of 6
99
erste Oxid-Schichtfirst oxide layer
1010
zweite Oxid-Schichtsecond oxide layer
1111
Austrittsöffnung in 6Outlet opening in 6
aa
Längsrichtung von 1Longitudinal direction of 1
bb
Winkel zwischen 11Angle between 11
cc
erste Kurve in Diagrammfirst curve in diagram
dd
zweite Kurve in Diagrammsecond curve in diagram
ee
Gewicht von Ruß im Verhältnis zum Ausgangsgewicht in DiagrammWeight of carbon black in relation to the initial weight in diagram
ff
Temperatur in DiagrammTemperature in diagram

Claims (10)

Einspritzventil für eine Brennkraftmaschine, umfassend einen Ventilkörper (5) mit einem Ventilkopf (6), welcher dazu ausgebildet ist, um zumindest abschnittsweise in einem Brennraum (4) der Brennkraftmaschine angeordnet oder diesem zumindest unmittelbar zugewandt zu sein, wobei der Ventilkopf (6) wenigstens bereichsweise mit einer ersten Oxid-Schicht (9) beschichtet ist, dadurch gekennzeichnet, dass
über der ersten Oxid-Schicht (9) eine zweite Oxid-Schicht (10) aus wenigstens einer oder mehreren Verbindungen der folgenden Gruppe angeordnet ist: Ceroxid (CeO2), Praseodymoxid (PrO2), Zirconiumoxid (ZrO2).Injection valve for an internal combustion engine, comprising a valve body (5) with a valve head (6), which is designed to at least partially arranged in a combustion chamber (4) of the internal combustion engine or at least directly facing it, wherein the valve head (6) at least partially coated with a first oxide layer (9), characterized in that
a second oxide layer (10) of at least one or more compounds of the following group is arranged above the first oxide layer (9): cerium oxide (CeO 2 ), praseodymium oxide (PrO 2 ), zirconium oxide (ZrO 2 ). Einspritzventil nach Anspruch 1,
dadurch gekennzeichnet, dass
die erste Oxid-Schicht (9) aus Titanoxid (TiO2) und/oder Aluminiumoxid (Al2O3) gebildet ist.Injection valve according to claim 1,
characterized in that
the first oxide layer (9) is formed from titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ). Einspritzventil nach Anspruch 1 oder 2,
dadurch gekennzeichnet, dass
die erste Oxid-Schicht (9) und/oder die zweite Oxid-Schicht (10) mit Kupferoxid (CuO) imprägniert sind/ist.Injection valve according to claim 1 or 2,
characterized in that
the first oxide layer (9) and / or the second oxide layer (10) is / are impregnated with copper oxide (CuO). Einspritzventil nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die erste Oxid-Schicht (9) und/oder die zweite Oxid-Schicht (10) mit wenigstens einem oder mehreren Elementen aus der folgenden Gruppe von Platinmetallen imprägniert sind/ist: Ruthenium (Ru), Osmium (Os), Rhodium (Rh),Iridium (Ir), Palladium (Pd),Platin (Pt). Injection valve according to one of the preceding claims,
characterized in that
the first oxide layer (9) and / or the second oxide layer (10) is / are impregnated with at least one or more elements from the following group of platinum metals: Ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt). Einspritzventil nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
der Ventilkopf (6) zumindest teilweise aus einem pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) oder aus einer Titanlegierung (Ti6Al4V) gebildet ist.Injection valve according to one of the preceding claims,
characterized in that
the valve head (6) is formed at least partially from a powder metallurgical Al-Si material (PEAK S250) or from a titanium alloy (Ti6Al4V). Verfahren zur Herstellung eines Einspritzventils (1) für eine Brennkraftmaschine insbesondere nach einem der vorhergehenden Ansprüche, umfassend einen Ventilkörper (5) mit einem Ventilkopf (6), welcher dazu ausgebildet ist, um zumindest abschnittsweise in einem Brennraum (4) der Brennkraftmaschine angeordnet oder diesem zumindest unmittelbar zugewandt zu sein, wobei der Ventilkopf (6) wenigstens bereichsweise mit einer ersten Oxid-Schicht (9) beschichtet wird,
dadurch gekennzeichnet, dass
über der ersten Oxid-Schicht (9) eine zweite Oxid-Schicht (10) aus wenigstens einer oder mehreren Verbindungen der folgenden Gruppe als Washcoat aufgebracht wird: Ceroxid (CeO2), Praseodymoxid (PrO2), Zirconiumoxid (ZrO2). Method for producing an injection valve (1) for an internal combustion engine, in particular according to one of the preceding claims, comprising a valve body (5) with a valve head (6) which is designed to be arranged at least in sections in or in a combustion chamber (4) of the internal combustion engine facing at least directly, wherein the valve head (6) is at least partially coated with a first oxide layer (9),
characterized in that
a second oxide layer (10) of at least one or more compounds of the following group is applied as washcoat over the first oxide layer (9): Ceria (CeO 2), praseodymium oxide (PrO 2), zirconium oxide (ZrO 2). Verfahren nach Anspruch 6,
dadurch gekennzeichnet, dass
die erste Oxid-Schicht (9) aus Titanoxid (TiO2) und/oder Aluminiumoxid (Al2O3) gebildet ist, wobei die erste Oxid-Schicht (9) mittels einer Micro Arc Oxidation (MAO) oder einer Plasmaelektrolytischen Oxidation (PEO) aufgebracht wird.Method according to claim 6,
characterized in that
the first oxide layer (9) is formed from titanium oxide (TiO 2 ) and / or aluminum oxide (Al 2 O 3 ), wherein the first oxide layer (9) by means of a micro arc oxidation (MAO) or a plasma electrolytic oxidation (PEO ) is applied. Verfahren nach Anspruch 6 oder 7,
dadurch gekennzeichnet, dass
die erste Oxid-Schicht (9) und/oder die zweite Oxid-Schicht (10) mit Kupferoxid (CuO) imprägniert werden/wird.Method according to claim 6 or 7,
characterized in that
the first oxide layer (9) and / or the second oxide layer (10) is / are impregnated with copper oxide (CuO). Verfahren nach einem der Ansprüche 6 bis 8,
dadurch gekennzeichnet, dass
die erste Oxid-Schicht (9) und/oder die zweite Oxid-Schicht (10) mit wenigstens einem Element aus der folgenden Gruppe von Platinmetallen imprägniert werden/wird: Ruthenium (Ru), Osmium (Os), Rhodium (Rh), Iridium (Ir), Palladium (Pd), Platin (Pt). Method according to one of claims 6 to 8,
characterized in that
the first oxide layer (9) and / or the second oxide layer (10) is impregnated with at least one of the following group of platinum metals: Ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt). Verfahren nach einem der Ansprüche 6 bis 9,
dadurch gekennzeichnet, dass
der Ventilkopf (6) zumindest teilweise aus einem pulvermetallurgischem Al-Si-Werkstoff (PEAK S250) oder aus einer Titanlegierung (Ti6Al4V) durch Schmelzschleudern gebildet wird.Method according to one of claims 6 to 9,
characterized in that
the valve head (6) is formed at least partially from a powder metallurgical Al-Si material (PEAK S250) or from a titanium alloy (Ti6Al4V) by melt-spinning.
EP14174075.3A 2013-07-17 2014-06-26 Injection valve for an internal combustion engine and method for producing an injection valve Active EP2826985B1 (en)

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RU153243U1 (en) 2015-07-10

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