WO2014102651A2 - Combustion chamber coating for engines - Google Patents

Combustion chamber coating for engines Download PDF

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Publication number
WO2014102651A2
WO2014102651A2 PCT/IB2013/060916 IB2013060916W WO2014102651A2 WO 2014102651 A2 WO2014102651 A2 WO 2014102651A2 IB 2013060916 W IB2013060916 W IB 2013060916W WO 2014102651 A2 WO2014102651 A2 WO 2014102651A2
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WO
WIPO (PCT)
Prior art keywords
coating
combustion chamber
engines
reduced emission
emission behavior
Prior art date
Application number
PCT/IB2013/060916
Other languages
German (de)
French (fr)
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WO2014102651A3 (en
Inventor
Werner Schuetze
Alexander Slaza
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Phitea GmbH
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Publication date
Application filed by Phitea GmbH filed Critical Phitea GmbH
Publication of WO2014102651A2 publication Critical patent/WO2014102651A2/en
Publication of WO2014102651A3 publication Critical patent/WO2014102651A3/en

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F02F3/12—Pistons  having surface coverings on piston heads
    • F02F3/14—Pistons  having surface coverings on piston heads within combustion chambers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C23C14/5813—Thermal treatment using lasers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction

Definitions

  • the invention relates to coated combustion chambers and pistons and to a method for coating combustion chambers and pistons.
  • the invention relates to coated combustion chambers that can be designed for HCCI combustion processes.
  • the invention equally also relates to a method for coating combustion chambers and pistons so that they are suitable for HCCI combustion processes.
  • the engines produced by means of the process according to the invention can also be advantageously used under other combustion processes.
  • combustion chamber surface is understood here as meaning the cylinder head surface, the valve surface, the land land and the piston surface.
  • the object of the invention is to provide an engine which has lower emissions of nitrogen oxides, carbon monoxide and hydrocarbons compared with engines known from the prior art.
  • the task is to increase the efficiency compared to gasoline or diesel engines according to the prior art.
  • Another aspect of the invention is to make engines known in the art suitable for use with metal pistons (aluminum pistons, cast irons, steel pistons) by surface modification for the HCCI combustion process.
  • the object of the invention is also to make engines with metal piston (aluminum piston, cast iron piston, steel piston) by surface modification suitable for the HCCI combustion process. This has the advantage that existing engine types can be retrofitted. For the method according to the invention, therefore, there are no technical obstacles to direct implementation in older and current engine generations, which allows a quick and easy market introduction.
  • Motor housings today consist of cast iron or aluminum alloys.
  • the valves are usually made of steel and have a significant share of the combustion chamber surface.
  • the pistons used are primarily aluminum pistons, cast pistons and steel pistons.
  • Aluminum pistons soften at temperatures above 450 ° C and release heat to the cylinder head. The firing temperature is therefore limited.
  • Cast iron or steel pistons reach higher temperatures between 550 and 650 ° C and can lead to misfires. They also give off heat to the cylinder wall.
  • the object of the invention is achieved with an engine according to claim 6, according to which the entire combustion chamber of the engine or at least a part thereof is coated with at least one coating, in which catalytically active particles are preferably introduced with a proportion of 1 to 10 percent by weight are.
  • the object of the invention is also achieved by a method according to claim 1, after the combustion chamber of an engine is at least partially coated, wherein the coating contains catalytically active particles.
  • the coating preferably contains, among other things, zirconium oxide which has thermally insulating properties and, according to various embodiments, particles of ⁇ 2 ⁇ 3- ⁇ 2, NiAl, Fe, Fe2O3, MgO, ThO2, Tantalum oxide or combinations thereof, preferably containing a total by weight of 1 to 10 percent by weight.
  • all particles can be used which have catalyzing properties, especially those which contain aluminum oxides, titanium oxides, carbons or carbides.
  • the coating preferably has a thermal resistance of less than 5 W / mK and, in one embodiment, is applied to more than 50% of the combustion chamber surface area. According to a preferred process, the coating is carried out by means of plasma spraying or by means of the PLD process. But other, known from the prior art methods are applicable.
  • the coating eg. the zirconium oxide layer, structured with the help of a laser
  • the pores of the zirconium oxide layer have dimensions between 0.5 and 10 ⁇ m, and preferably between 1 and 3 ⁇ m. Surprisingly, it has been shown that in these areas a particularly good penetration of the gas particles and decomposition is achieved by means of the catalytically active particles and also a sufficient strength of the surface is maintained even for long periods of operation of the engine.
  • the internal oxidation is used in alloys in order to influence the porosity.
  • a temperature is selected in the manufacturing process, which can oxidize a proportion of easily oxidizable metal particles and not oxidize a different proportion of metal particles.
  • Acid scrubbing removes the unoxidized metal from the coating and leaves a porous structure behind. With such a procedure can help with the particle size, the porosity can be optimally adjusted to the requirements of HCCI combustion.
  • FIG. 1 is a piston with a modified combustion chamber surface
  • Figure 2 is a schematic representation of the layer structure for the
  • FIG. 1 shows a piston whose surface 12 is part of the combustion chamber surface 1.
  • the piston has a total of three layers of zirconia, wherein the surface layer 12 is microstructured.
  • Adjacent to the material of the piston 20 is a matching layer 10 of zirconia, which is designed so that they are particularly good and durable on the surface of the Base material of the piston 20 can adhere.
  • a leveling layer Between the porous surface 12 and the matching layer 10 is still a leveling layer, which causes a good adhesion of the porous surface 12 to the matching layer 10 and thus to the material of the piston 20.
  • FIG. 2 shows the schematic layer structure of the combustion chamber surface 1 of the combustion chamber coating according to the invention.
  • the coatings 10, 11, 12 contain zirconium oxide with a thermal conductivity of about 2.5 W / mK.
  • the zirconium oxide layer has a pore size of between 0.5 and 10 ⁇ m by the application method.
  • catalytic particles 14 are introduced, which are partially accessible to the fuel gases in the application via the pores 13.
  • the surface of the zirconium oxide layer is by means of
  • a laser is structured.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion Methods Of Internal-Combustion Engines (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Catalysts (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Reduced emission engine and method for producing the same, at least one of the partial surfaces of the combustion chamber surface (1) having a coating (12) that contains catalytically active particles (14). Fig.

Description

Brennraumbeschichtung für Motoren Beschreibung:  Combustion chamber coating for engines Description:
Die Erfindung betrifft beschichtete Brennräume und Kolben sowie ein Verfahren zur Beschichtung von Brennräumen und Kolben. The invention relates to coated combustion chambers and pistons and to a method for coating combustion chambers and pistons.
Insbesondere betrifft die Erfindung beschichtete Brennräume, welche für HCCI Verbrennungsverfahren ausgelegt bzw. verwendet werden können. Die Erfindung betrifft gleichermaßen auch ein Verfahren zur Beschichtung von Brennräume und Kolben, sodass diese für HCCI Verbrennungsverfahren geeignet sind. In particular, the invention relates to coated combustion chambers that can be designed for HCCI combustion processes. The invention equally also relates to a method for coating combustion chambers and pistons so that they are suitable for HCCI combustion processes.
Die mit Hilfe des erfindungsgemäßen Verfahrens hergestellten Motoren können jedoch auch unter anderen Verbrennungsverfahren vorteilhaft verwendet werden. However, the engines produced by means of the process according to the invention can also be advantageously used under other combustion processes.
Das Wesen der HCCI Motoren ist die Kompressionszündung und rückstandsfreie Verbrennung sowohl für Diesel- als auch für Benzin. Um diesen Zweck zu erfüllen, müssen Brennstoffaufbereitung, Brennverfahren und die Brennraumoberfläche optimal zusammen arbeiten. Unter dem Begriff Brennraumoberfläche werden hier die Zylinderkopffläche, die Ventilfläche, der Feuersteg und die Kolbenfläche verstanden. The essence of HCCI engines is compression ignition and residue-free combustion for both diesel and gasoline. To meet this purpose, fuel conditioning, combustion process and the combustion chamber surface must work together optimally. The term combustion chamber surface is understood here as meaning the cylinder head surface, the valve surface, the land land and the piston surface.
Der Nachteil herkömmlicher HCCI Motoren besteht in dem gegenüber Otto- oder Dieselmotoren höherem Kohlenmonoxid sowie Kohlenwasserstoff Ausstoß. The disadvantage of conventional HCCI engines is in comparison to gasoline or diesel engines higher carbon monoxide and hydrocarbon emissions.
Die Aufgabe der Erfindung besteht darin, einen Motor bereitzustellen, welcher einen gegenüber aus dem Stand der Technik bekannten Motoren geringeren Ausstoß von Stickoxiden, Kohlenmonoxid sowie Kohlenwasserstoff besitzt. Zudem besteht die Aufgabe darin, den Wirkungsgrad gegenüber Otto- oder Dieselmotoren gemäß dem Stand der Technik zu steigern. Ein weiterer Aspekt der Erfindung besteht darin, aus dem Stand der Technik bekannte Motoren mit Metallkolben (Aluminiumkolben, Gußkolben, Stahlkolben) durch Oberflächenmodifizierung für das HCCI- Verbrennungsverfahren tauglich zu machen. Die Aufgabe der Erfindung besteht darüber hinaus darin, Motoren mit Metall kolben (Aluminiumkolben, Gusskolben, Stahlkolben) durch Oberflächenmodifizierung für das HCCI-Verbrennungsverfahren tauglich zu machen. Das hat den Vorteil, dass bestehende Motortypen umgerüstet werden können. Für das erfindungsgemäße Verfahren bestehen deshalb keine technischen Hindernisse zur direkten Umsetzung bei älteren und aktuellen Motorengenerationen, was eine schnelle und unkomplizierte Markteinführung ermöglicht. The object of the invention is to provide an engine which has lower emissions of nitrogen oxides, carbon monoxide and hydrocarbons compared with engines known from the prior art. In addition, the task is to increase the efficiency compared to gasoline or diesel engines according to the prior art. Another aspect of the invention is to make engines known in the art suitable for use with metal pistons (aluminum pistons, cast irons, steel pistons) by surface modification for the HCCI combustion process. The object of the invention is also to make engines with metal piston (aluminum piston, cast iron piston, steel piston) by surface modification suitable for the HCCI combustion process. This has the advantage that existing engine types can be retrofitted. For the method according to the invention, therefore, there are no technical obstacles to direct implementation in older and current engine generations, which allows a quick and easy market introduction.
Motorengehäuse bestehen heutzutage aus Gusseisen oder aus Aluminiumlegierungen. Die Ventile bestehen in der Regel aus Stahl und haben einen beträchtlichen Anteil an der Brennraumoberfläche. Als Kolben werden vor allem Aluminiumkolben, Gusskolben und Stahlkolben verwendet. Motor housings today consist of cast iron or aluminum alloys. The valves are usually made of steel and have a significant share of the combustion chamber surface. The pistons used are primarily aluminum pistons, cast pistons and steel pistons.
Aluminiumkolben erweichen bei Temperaturen von über 450 °C und geben Wärme an den Zylinderkopf ab. Die Brenntemperatur ist daher beschränkt. Aluminum pistons soften at temperatures above 450 ° C and release heat to the cylinder head. The firing temperature is therefore limited.
Guss- oder Stahlkolben erreichen höhere Temperaturen zwischen 550 und 650 °C und können zu Fehlzündungen führen. Sie geben ebenfalls Wärme an die Zylinderwand ab. Cast iron or steel pistons reach higher temperatures between 550 and 650 ° C and can lead to misfires. They also give off heat to the cylinder wall.
Die Aufgabe der Erfindung wird mit einem Motor gemäß Anspruch 6 gelöst, gemäß dem der gesamte Brennraum des Motors bzw. zumindest ein Teil davon mit wenigstens einer Beschichtung überzogen ist, in welche katalytisch wirksame Partikel mit vorzugsweise einem Anteil von 1 bis 10 Gewichts-Prozent eingebracht sind. The object of the invention is achieved with an engine according to claim 6, according to which the entire combustion chamber of the engine or at least a part thereof is coated with at least one coating, in which catalytically active particles are preferably introduced with a proportion of 1 to 10 percent by weight are.
Die Aufgabe der Erfindung wir auch durch ein Verfahren gemäß Anspruch 1 gelöst, nachdem der Brennraum eines Motors wenigstens teilweise beschichtet wird, wobei die Beschichtung katalytisch wirksame Partikel enthält. The object of the invention is also achieved by a method according to claim 1, after the combustion chamber of an engine is at least partially coated, wherein the coating contains catalytically active particles.
Vorzugsweise enthält die Beschichtung unter anderem Zirkonoxid, welches thermisch isolierende Eigenschaften besitzt und gemäß verschiedenen Ausführungsformen Partikel aus ΑΙ2Ο3-ΤΪΟ2, NiAl, Fe, Fe2O3, MgO, ThO2, Tantaloxid oder Kombinationen hieraus, vorzugsweise mit einem Gewichtsanteil von insgesamt 1 bis 10 Gewichts-Prozent enthält. The coating preferably contains, among other things, zirconium oxide which has thermally insulating properties and, according to various embodiments, particles of ΑΙ2Ο3-ΤΪΟ2, NiAl, Fe, Fe2O3, MgO, ThO2, Tantalum oxide or combinations thereof, preferably containing a total by weight of 1 to 10 percent by weight.
Prinzipiell sind sämtliche Partikel verwendbar, welche katalysierende Eigenschaften besitzen, vor allem auch solche, welche Aluminium-Oxide, Titan-Oxide, Kohlenstoffe bzw. Carbide enthalten.  In principle, all particles can be used which have catalyzing properties, especially those which contain aluminum oxides, titanium oxides, carbons or carbides.
Zirkonoxid ist nicht nur thermisch sehr stabil sondern hat auch eine geringe thermische Leitfähigkeit. Hierdurch können die Motoren bei höheren Brennraum- Temperaturen betrieben werden. Damit ein HCCI Verbrennungsverfahren effizient betrieben werden kann, hat die Beschichtung bevorzugt einen Wärmeleitwiderstand von weniger als 5 W/mK und ist gemäß einer Ausführungsform auf mehr als 50% der Brennraum-Oberfläche aufgebracht. Gemäß einem bevorzugten Verfahrensprozess wird die Beschichtung mit Hilfe von Plasmaspritzen oder mit Hilfe des PLD- Verfahrens vorgenommen. Aber auch andere, aus dem Stand der Technik bekannte Verfahren sind anwendbar. Zirconia is not only very thermally stable but also has a low thermal conductivity. This allows the motors to be operated at higher combustion chamber temperatures. For an HCCI combustion process to be efficiently operated, the coating preferably has a thermal resistance of less than 5 W / mK and, in one embodiment, is applied to more than 50% of the combustion chamber surface area. According to a preferred process, the coating is carried out by means of plasma spraying or by means of the PLD process. But other, known from the prior art methods are applicable.
Um eine besonders große Oberfläche und eine möglichst große Porosität zu erreichen, wird die Beschichtung, also z.B. die Zirkonoxidschicht, mit Hilfe eines Lasers strukturiert In order to achieve a particularly large surface area and as large a porosity as possible, the coating, eg. the zirconium oxide layer, structured with the help of a laser
Gemäß einer bevorzugten Ausführungsvariante besitzen die Poren der Zirkonoxidschicht Abmessungen zwischen 0,5 und 10 |vim und bevorzugt zwischen 1 und 3. |vim. Überraschender Weise hat sich gezeigt, dass in diesen Bereichen eine besonders gute Eindringung der Gasteilchen und Zerlegung mit Hilfe der katalytisch wirkenden Partikel erreicht wird und zudem eine ausreichende Festigkeit der Oberfläche auch für lange Betriebszeiten des Motors gewahrt bleibt. According to a preferred embodiment variant, the pores of the zirconium oxide layer have dimensions between 0.5 and 10 μm, and preferably between 1 and 3 μm. Surprisingly, it has been shown that in these areas a particularly good penetration of the gas particles and decomposition is achieved by means of the catalytically active particles and also a sufficient strength of the surface is maintained even for long periods of operation of the engine.
Gemäß einer weiteren Ausführungsform wird die innere Oxidation bei Legierungen eingesetzt um die Porosität zu beeinflussen. Dabei wird im Herstellungsverfahren eine Temperatur gewählt, die einen Anteil leichter oxidierbarer Metallpartikel oxidieren lässt und einen anderen Anteil von Metallpartikeln nicht oxidieren lässt. Durch eine Säure-Wäsche wird der Beschichtung das nicht-oxidierte Metall entzogen und eine poröse Struktur bleibt zurück. Mit einem solchen Verfahren kann mit Hilfe der Partikelgröße die Porosität optimal auf die Erfordernisse der HCCI Verbrennung eingestellt werden. According to a further embodiment, the internal oxidation is used in alloys in order to influence the porosity. In this case, a temperature is selected in the manufacturing process, which can oxidize a proportion of easily oxidizable metal particles and not oxidize a different proportion of metal particles. Acid scrubbing removes the unoxidized metal from the coating and leaves a porous structure behind. With such a procedure can help with the particle size, the porosity can be optimally adjusted to the requirements of HCCI combustion.
Durch die in die Beschichtung eingebrachten katalytisch wirkenden Partikel werden die auf die Wirkoberfläche auftreffenden Moleküle aufgespalten und sofort verbrannt (umgekehrtes Fischer-Tropsch-, Bergius-Verfahren). As a result of the catalytically active particles introduced into the coating, the molecules impinging on the active surface are split and immediately burnt (reverse Fischer-Tropsch, Bergius process).
Weitere Einzelheiten der Erfindung gehen aus den Zeichnungen anhand der Beschreibung hervor. Further details of the invention will become apparent from the drawings with reference to the description.
Dabei sollen die in den beschriebenen Ausführungsbeispielen offenbarten Merkmalskombinationen nicht limitierend auf die Erfindung wirken, vielmehr sind auch die Merkmale der unterschiedlichen Ausführungen miteinander kombinierbar. In den Zeichnungen zeigen In this case, the feature combinations disclosed in the described embodiments should not limit the invention, but also the features of the different embodiments are combined. In the drawings show
Figur 1 ist ein Kolben mit modifizierter Brennraumoberfläche, FIG. 1 is a piston with a modified combustion chamber surface;
Figur 2 ist eine schematische Darstellung des Schichtenaufbaus für die  Figure 2 is a schematic representation of the layer structure for the
Brennraumoberfläche.  Combustion chamber surface.
Bezugszeichenliste: LIST OF REFERENCE NUMBERS
I Brennraumoberfläche I combustion chamber surface
10 Anpassungsschicht mit Zirkonoxid  10 matching layer with zirconia
I I Ausgleichsschicht  I I leveling layer
12 Poröse Oberfläche  12 Porous surface
13 Poren  13 pores
14 Katalytisch wirkende Partikel  14 catalytic particles
Figur 1 zeigt einen Kolben, dessen Oberfläche 12 Teil der Brennraumoberfläche 1 ist. Der Kolben weist insgesamt 3 Schichten aus Zirkonoxid auf, wobei die Oberflächenschicht 12 mikrostrukturiert ist. An das Material des Kolbens 20 angrenzend befindet sich eine Anpassungsschicht 10 aus Zirkonoxid, welche so ausgebildet ist, dass sie besonders gut und langlebig an der Oberfläche des Grundmaterials des Kolbens 20 anhaften kann. Zwischen der porösen Oberfläche 12 und der Anpassungsschicht 10 befindet sich noch eine Ausgleichsschicht, welche eine gute Haftung der porösen Oberfläche 12 an den Anpassungsschicht 10 und damit an dem Material des Kolbens 20 bewirkt. FIG. 1 shows a piston whose surface 12 is part of the combustion chamber surface 1. The piston has a total of three layers of zirconia, wherein the surface layer 12 is microstructured. Adjacent to the material of the piston 20 is a matching layer 10 of zirconia, which is designed so that they are particularly good and durable on the surface of the Base material of the piston 20 can adhere. Between the porous surface 12 and the matching layer 10 is still a leveling layer, which causes a good adhesion of the porous surface 12 to the matching layer 10 and thus to the material of the piston 20.
Figur 2 zeigt den schematischen Schichtaufbau der Brennraumoberfläche 1 der erfindungsgemäßen Brennraumbeschichtung. Die Beschichtungen 10, 11 , 12 enthalten Zirkonoxid mit einem Wärmeleitwiderstand von etwa 2,5 W/mK. Dabei verfügt die Zirkonoxidschicht durch das Aufbringungsverfahren eine Abmessung der Poren von zwischen 0,5 und 10 |vim. In der Zirkonoxidschicht sind katalytisch wirkende Partikel 14 eingebracht, welche für die Brennstoffgase im Anwendungsfall teilweise über die Poren 13 zugänglich sind. Zusätzlich zu den Poren 13 ist die Oberfläche der Zirkonoxidschicht mittels FIG. 2 shows the schematic layer structure of the combustion chamber surface 1 of the combustion chamber coating according to the invention. The coatings 10, 11, 12 contain zirconium oxide with a thermal conductivity of about 2.5 W / mK. The zirconium oxide layer has a pore size of between 0.5 and 10 μm by the application method. In the zirconium oxide layer, catalytic particles 14 are introduced, which are partially accessible to the fuel gases in the application via the pores 13. In addition to the pores 13, the surface of the zirconium oxide layer is by means of
eines Lasers strukturiert ist. a laser is structured.

Claims

Ansprüche: Claims:
1 . Verfahren zur Herstellung von Motoren mit reduziertem Emissionsverhalten wobei die Brennraumoberfläche (1 ) eines Motors wenigstens teilweise beschichtet wird, dadurch gekennzeichnet, dass die Beschichtung (12) katalytisch wirksame Partikel (14) enthält. 1 . Method for producing engines with reduced emission behavior, wherein the combustion chamber surface (1) of a motor is at least partially coated, characterized in that the coating (12) contains catalytically active particles (14).
2. Verfahren zur Herstellung von Motoren mit reduziertem Emissionsverhalten, nach Anspruch 1 , dadurch gekennzeichnet, dass die Beschichtung (12) Poren (13) mit gegenüber herkömmlichen metallischen Brennraumoberflächen vergrößerten Abmessungen aufweist. 2. A method for the production of engines with reduced emission behavior, according to claim 1, characterized in that the coating (12) has pores (13) with respect to conventional metallic combustion chamber surfaces enlarged dimensions.
3. Verfahren zur Herstellung von Motoren mit reduziertem Emissionsverhalten nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die Beschichtung (12) einen Wärmeleitwiderstand von weniger als 5 W/mK hat. 3. A process for the production of engines with reduced emission behavior according to any one of claims 1 or 2, characterized in that the coating (12) has a thermal conductivity of less than 5 W / mK.
4. Verfahren zur Herstellung von Motoren mit reduziertem Emissionsverhalten nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Beschichtung (12) mittels Plasmaspritzen oder PLD Puls-Laser Deposition Verfahren aufgebracht ist. 4. A process for the production of engines with reduced emission behavior according to one of the preceding claims, characterized in that the coating (12) by means of plasma spraying or PLD pulse laser deposition method is applied.
5. Verfahren zur Herstellung von Motoren mit reduziertem Emissionsverhalten nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Beschichtung (12) durch die Verwendung eines Lasers Strukturiert bzw. oberflächenmodifiziert ist. 5. A process for the production of engines with reduced emission behavior according to one of the preceding claims, characterized in that the coating (12) by the use of a laser is structured or surface-modified.
6. Motor mit reduziertem Emissionsverhalten, welcher zumindest in einem Teilbereich der Brennraumoberfläche (1 ) mit einer Beschichtung (12) versehen ist, dadurch gekennzeichnet, dass die Beschichtung (12) katalytisch wirkende Partikel (14) enthält. 6. engine with reduced emission behavior, which is provided at least in a partial region of the combustion chamber surface (1) with a coating (12), characterized in that the coating (12) contains catalytically active particles (14).
7. Motor mit reduziertem Emissionsverhalten nach Anspruch 6, dadurch gekennzeichnet, dass die Beschichtung (12) eine gegenüber herkömmlichen metallischen Brennraumoberflächen (1 ) vergrößerte Abmessung der Poren (13) aufweist. A reduced emission engine according to claim 6, characterized in that the coating (12) is one over conventional ones metallic combustion chamber surfaces (1) enlarged dimension of the pores (13).
8. Motor mit reduziertem Emissionsverhalten nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass die Beschichtung (12) einen Wärmeleitwiderstand von weniger als 5 W/mK aufweist. 8. Engine with reduced emission behavior according to one of claims 7 or 8, characterized in that the coating (12) has a thermal resistance of less than 5 W / mK.
9. Motor mit reduziertem Emissionsverhalten nach einem oder mehreren der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass die Oberfläche der Beschichtung (12) laserstrukturiert ist. 9. engine with reduced emission behavior according to one or more of claims 6 to 8, characterized in that the surface of the coating (12) is laser-structured.
10. Kolben für einen Motor nach Anspruch 6, wobei der Kolben zumindest auf einem Teilbereich eine Beschichtung (12) aufweist, in welche katalytisch wirkende Partikel (14) eingebracht sind. 10. Piston for an engine according to claim 6, wherein the piston has at least on a partial area a coating (12), in which catalytically active particles (14) are introduced.
PCT/IB2013/060916 2012-12-28 2013-12-13 Combustion chamber coating for engines WO2014102651A2 (en)

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