EP1340834A2 - Coated running surfaces of combustion-engine cylinders and process of its manufacture - Google Patents

Coated running surfaces of combustion-engine cylinders and process of its manufacture Download PDF

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Publication number
EP1340834A2
EP1340834A2 EP03405004A EP03405004A EP1340834A2 EP 1340834 A2 EP1340834 A2 EP 1340834A2 EP 03405004 A EP03405004 A EP 03405004A EP 03405004 A EP03405004 A EP 03405004A EP 1340834 A2 EP1340834 A2 EP 1340834A2
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EP
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Prior art keywords
weight
tread layer
cylinder
cylinder tread
plasma
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Granted
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EP03405004A
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German (de)
French (fr)
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EP1340834B1 (en
EP1340834A3 (en
Inventor
Gérard BARBEZAT
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Oerlikon Metco AG
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Sulzer Metco AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • 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
    • C23C4/06—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
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes

Definitions

  • the invention relates to a cylinder tread layer for reciprocating engines according to Claim 1 and a method for producing the same according to claim 11.
  • the objective can be, for example, that the Oil change intervals can be extended to 100,000 km without oil in between needs to be refilled.
  • the surface quality (topography) the cylinder tread layer has a decisive influence on oil consumption Has.
  • a plasma coating method is known from publication US Pat. No. 5,766,693 known in which mixed layers of metals and metal oxides in their lowest oxidation levels are generated in which the metal and the metal oxide regions are separated from each other.
  • the proposed measures can neither reduce oil consumption the tribological properties are significantly reduced.
  • the object of the invention is to overcome the disadvantages of the prior art the technology to overcome and an improved cylinder tread layer for Reciprocating engines to create what favorable conditions for a low Oil consumption offers and at the same time has good tribological properties.
  • a Another object of the invention is a method for producing such Specify cylinder tread layers.
  • the arithmetic mean roughness R a mentioned in the claims is also referred to briefly as the mean roughness value or as the CLA (Center Line Average). It is defined as the height of a rectangle, the length of which corresponds to the length of a given measurement section and whose area is equal to the area between the profile center line and the surface profile, while the average roughness depth R z is defined as the mean value of the individual roughness depths of five successive individual measurement sections (see : Encyclopedia of Natural Sciences and Technology, Volume 3, Verlag Moderne Industrie, Landsberg a.Lech, Germany 1980, ISBN 3-478-41820-X, pages 3063 to 3065).
  • CLA Center Line Average
  • Preferred embodiments of the tread layer according to the invention are circumscribed in the dependent claims 2 to 10.
  • individual parameters are specified with which the porosity the cylinder tread layer can be influenced in a targeted manner.
  • the measures according to the invention ensure on the one hand that to absorb the oil to form an oil film between the piston or piston rings and cylinder wall and thus sufficient to maintain the good tribological properties Pores are present.
  • the absolute oil consumption can the very small pores (cavities) are kept small.
  • the layer according to the invention thus has a porous one Basic structure, in which the size of the individual pores within a defined Range.
  • the mechanical post-processing means that the Open pores on the surface.
  • the invention is based on the surprising finding that there is an important mutual technical relationship between the arithmetic mean roughness R a and the behavior of the layers.
  • the arithmetic mean roughness R a is plotted in the abscissa (x-axis), the performance level L of the layers - qualitative, not quantitative - in the ordinate.
  • the performance level L is the integral of the coefficient of friction, oil consumption and wear resistance. If the arithmetic mean roughness R a is too low , there is a risk of adhesive wear, so-called “scuffing” (area A in FIG. 1). If the arithmetic mean roughness R a is too great, the oil consumption increases in an unacceptable manner (region B in FIG. 1).
  • the desired improvement can be achieved by combining the features mentioned in the characterizing part of claim 1.
  • the cylinder tread layer applied by means of a plasma spraying device 1 is provided with a large number of open pores 2, 3, 4.
  • the pores have a size between approx. 2 and 30 ⁇ m, the major part between approx. 5 and 20 ⁇ m is big.
  • the degree of porosity of the layer i.e. the proportion of pores in the total Shift volume, is between 1 and 5%.
  • the areal movement also moves Proportion of pores 2, 3, 4 in the entire surface of cylinder surface layer 1 between the above 1 and 5%.
  • the cylinder tread layer 1 is constructed that there are practically exclusively pores 2, 3, 4 with a dimension ⁇ 100 ⁇ m.
  • the cylinder tread layer 1 has a bound oxygen content of 0.5 to 8% by weight, the bound oxygen forming FeO and Fe 3 O 4 crystals with iron, which act as solid lubricants.
  • the Fe 2 O 3 content is preferably less than 0.2% by weight.
  • the amount of oxides formed can be further influenced by enriching or reducing the air flowing through the cylinder bore to be coated with nitrogen or oxygen during the coating process.
  • the proportion of oxygen bound in the cylinder tread layer 1 can also be influenced by the speed of the air flowing through the cylinder bore to be coated during the coating process. When the air is replaced by pure oxygen, the bound amount of oxygen in the layer is reduced by a factor of about two.
  • the cylinder tread layer 1 preferably contains between 1.2 and 3.5% by weight Manganese and 0.05 to 0.4% by weight sulfur.
  • the pores 2, 3, 4 are distributed stochastically in terms of area as well as size.
  • a rotating plasma spray device is preferably used to apply the layer, so that the engine block to be coated can rest during the coating process.
  • the cylinder tread layer 1 is reworked mechanically, in particular by honing, preferably diamond honing, until the roughness of the cylinder tread layer 1 has an arithmetic mean roughness R a of 0.02 to 0.4 ⁇ m and an average roughness depth R z of 0.5 to 5 ⁇ m, preferably set to an arithmetic mean roughness R a of 0.05 to 0.2 ⁇ m and an average roughness depth R z of 1 to 3 ⁇ m.
  • the proportion of pores 2, 3, 4 in the total layer volume (degree of porosity), such as The size (dimension) of the pores 2, 3, 4 can also be changed by changing the coating parameters and the particle size of the coating powder can be influenced in a targeted manner.
  • the enthalpy of the plasma plays a decisive role here, which is mainly due to the hydrogen content in the plasma gas and the plasma flow is determined.
  • the cylinder tread layer 1 by plasma spraying a gas or water atomized coating powder with a particle size between 5 and 100 microns, preferably from 10 and 50 microns, the Spraying distance, i.e. the distance between the powder injector of the plasma spraying device and the surface to be coated is 20 to 50 mm.
  • Argon with a proportion of 0.5 to 5 NLPM is expediently used as the plasma gas (Normal liters per minute) uses hydrogen.
  • the plasma flow is convenient between 100 and 500 amps, preferably between 260 and 360 amps, at one Voltage between 35 and 45 volts.
  • Such a cylinder tread layer 1 is particularly suitable for application on substrates made of cast aluminum alloys, wrought aluminum alloys, cast iron with lamellar graphite, Cast iron with vermicular graphite, cast iron with spheroidal graphite or magnesium casting alloys.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Combustion Methods Of Internal-Combustion Engines (AREA)

Abstract

Cylinder running surface layer applied by plasma spraying has a number of open pores and has a degree of porosity of 0.5-10%. The average pore size is 1-50 microns. The pores are distributed dimensionally or in a planar manner in the running surface layer surface. The cylinder running surface layer surface contains 0.5-8 wt.% oxygen with iron oxide (FeO) and iron oxide (Fe3O4) crystals to form a solid lubricant. The roughness of the cylinder running surface layer is adjusted to 0.02-0.4 microns (average roughness) with a depth of 0.5-5 microns. An Independent claim is also included for a process for the production of a cylinder running surface layer. Preferred Features: The cylinder running surface layer has a Vickers micro-hardness HV0.3 of 350-550 N/mm squared. The cylinder running surface layer has the following composition: 0.05-1.5 wt.% carbon (C), 0.05-3.5 wt.% manganese (Mn), 0.05-18 wt.% chromium (Cr), 0.01-1 wt.% silicon (Si), 0.001-0.4 wt.% sulfur (S) and a balance of iron (Fe).

Description

Die Erfindung betrifft eine Zylinderlaufflächenschicht für Hubkolbenmotoren gemäss Anspruch 1 sowie ein Verfahren zur Herstellung derselben gemäss Anspruch 11.The invention relates to a cylinder tread layer for reciprocating engines according to Claim 1 and a method for producing the same according to claim 11.

Nachdem bei den Motorenölen in der letzten Zeit markante Fortschritte in Bezug auf deren Lebensdauer erreicht wurden, wäre es nun wünschenswert, den Ölverbrauch bei Hubkolbenmotoren soweit zu reduzieren, dass die Ölwechselintervalle weiter ausgedehnt werden können. Die Zielsetzung kann beispielsweise darin bestehen, dass die Ölwechselintervalle auf 100'000 km ausgedehnt werden, ohne dass dazwischen Öl nachgefüllt werden muss. Es ist bekannt, dass die Oberflächenbeschaffenheit (Topographie) der Zylinderlaufflächenschicht einen entscheidenden Einfluss auf den Ölverbrauch hat. Obwohl auch schon bis anhin hohe Oberflächengüten durch Honen erreicht werden konnten, weisen die heutigen Zylinderlaufflächenschichten zumeist eine nicht näher spezifizierte Porosität auf, bzw. sie sind zum Mindesten mit einzelnen Poren versehen, die relativ gross sind und den Ölverbrauch negativ beeinflussen.Having made striking progress in terms of engine oils lately over their lifespan, it would now be desirable to reduce oil consumption for reciprocating engines to be reduced to such an extent that the oil change intervals are extended further can be. The objective can be, for example, that the Oil change intervals can be extended to 100,000 km without oil in between needs to be refilled. It is known that the surface quality (topography) the cylinder tread layer has a decisive influence on oil consumption Has. Although high surface qualities have already been achieved by honing today's cylinder tread layers usually have one Porosity unspecified, or they are at least with single pores which are relatively large and have a negative impact on oil consumption.

Aus der Veröffentlichung WO 99/05339 A1 ist bereits ein thermisches Plasmabeschichtungsverfahren für Innenräume, insbesondere für Gleitlager bekannt, welches darauf abzielt, eine Oxidbildung in dem an sich oxidierbaren Beschichtungswerkstoff nach Möglichkeit zu verhindern, da derartige Oxideinschlüsse eine unerwünschte Porosität begünstigen. Es wird eine Gesamtporosität von weniger als 3 % angestrebt, wobei die Poren weitgehend geschlossen sein sollen. Weiter wird vorgeschlagen, die aufgebrachte Schicht auf eine arithmetische Mittenrauheit (Mittenrautiefe) Ra von 4 bis 30 µm aufzurauen. Durch die vorgeschlagenen Massnahmen können jedoch weder der Ölverbrauch wesentlich gesenkt noch die tribologischen Eigenschaften wesentlich verbessert werden.From publication WO 99/05339 A1, a thermal plasma coating process for interiors, in particular for plain bearings, is already known, which aims to prevent oxide formation in the coating material, which can be oxidized per se, if possible, since such oxide inclusions favor an undesired porosity. A total porosity of less than 3% is aimed for, the pores being said to be largely closed. It is also proposed to roughen the applied layer to an arithmetic mean roughness (center roughness depth) R a of 4 to 30 μm. However, the proposed measures can neither significantly reduce oil consumption nor significantly improve tribological properties.

Weiter ist aus der Veröffentlichung US 5 766 693 A ein Plasmabeschichtungsverfahren bekannt, bei welchem Mischschichten von Metallen und Metalloxiden in deren niedrigsten Oxidationsstufen erzeugt werden, in denen die Metall- und die Metalloxidregionen voneinander getrennt sind. Es werden ein Metalloxidgehalt von höchstens 30 %, ein Porositätsgrad von 3 bis 10 %, eine Porengrösse von 1 bis 6 µm und eine Oberflächenrauheit (arithmetische Mittenrauheit) von 3,8 bis 14 µm (150 bis 550 µin) angestrebt. Durch die vorgeschlagenen Massnahmen können jedoch weder der Ölverbrauch wesentlich gesenkt noch die tribologischen Eigenschaften wesentlich verbessert werden.Furthermore, a plasma coating method is known from publication US Pat. No. 5,766,693 known in which mixed layers of metals and metal oxides in their lowest oxidation levels are generated in which the metal and the metal oxide regions are separated from each other. There is a metal oxide content of at most 30%, a degree of porosity of 3 to 10%, a pore size of 1 to 6 µm and a surface roughness (arithmetic mean roughness) of 3.8 to 14 µm (150 to 550 µin). However, the proposed measures can neither reduce oil consumption the tribological properties are significantly reduced.

Die Aufgabe der Erfindung besteht nun darin, die erwähnten Nachteile des Standes der Technik zu überwinden und eine verbesserte Zylinderlaufflächenschicht für Hubkolbenmotoren zu schaffen, welche günstige Voraussetzungen für einen niedrigen Ölverbrauch bietet und gleichzeitig gute tribologische Eigenschaften aufweist. Eine weitere Aufgabe der Erfindung besteht darin, ein Verfahren zur Erzeugung einer derartiger Zylinderlaufflächenschichten anzugeben.The object of the invention is to overcome the disadvantages of the prior art the technology to overcome and an improved cylinder tread layer for Reciprocating engines to create what favorable conditions for a low Oil consumption offers and at the same time has good tribological properties. A Another object of the invention is a method for producing such Specify cylinder tread layers.

Diese Aufgabe wird hinsichtlich der Zylinderlaufflächenschicht durch die Kombination der im Kennzeichen des Anspruchs 1 angegeben Merkmale gelöst, während im Kennzeichen des Anspruchs 10 die Verfahrensschritte zur Erzeugung einer derartigen Zylinderlaufflächenschicht angeführt sind.This task is accomplished with the combination regarding the cylinder tread layer the features specified in the characterizing part of claim 1 solved, while in The method steps for generating such a Cylinder tread layer are listed.

Die in den Ansprüchen erwähnte arithmetische Mittenrauheit Ra wird auch kurz als Mittenrauhwert oder als CLA (Center Line Average) bezeichnet. Sie ist definiert als die Höhe eines Rechteckes, dessen Länge der Länge einer gegebenen Messtrecke entspricht und dessen Fläche gleich der Fläche zwischen der Profilmittellinie und dem Oberflächenprofil ist, während die gemittelte Rautiefe Rz definiert ist als der Mittelwert der Einzelrautiefen von fünf aufeinanderfolgenden Einzelmessstrecken (siehe: Enzyklopädie Naturwissenschaft und Technik, Band 3, Verlag Moderne Industrie, Landsberg a. Lech, Deutschland 1980, ISBN 3-478-41820-X, Seiten 3063 bis 3065).The arithmetic mean roughness R a mentioned in the claims is also referred to briefly as the mean roughness value or as the CLA (Center Line Average). It is defined as the height of a rectangle, the length of which corresponds to the length of a given measurement section and whose area is equal to the area between the profile center line and the surface profile, while the average roughness depth R z is defined as the mean value of the individual roughness depths of five successive individual measurement sections (see : Encyclopedia of Natural Sciences and Technology, Volume 3, Verlag Moderne Industrie, Landsberg a.Lech, Germany 1980, ISBN 3-478-41820-X, pages 3063 to 3065).

Bevorzugte Ausführungsformen der erfindungsgemässen Laufflächenschicht sind in den abhängigen Ansprüchen 2 bis 10 umschrieben. In den abhängigen Verfahrensansprüchen 12 bis 21 werden einzelne Parameter angegeben, mit denen die Porosität der Zylinderlaufflächenschicht gezielt beeinflusst werden kann. Preferred embodiments of the tread layer according to the invention are circumscribed in the dependent claims 2 to 10. In the dependent procedural claims 12 to 21 individual parameters are specified with which the porosity the cylinder tread layer can be influenced in a targeted manner.

Durch die erfindungsgemässen Massnahmen wird einerseits sichergestellt, dass zur Aufnahme des Öls zur Bildung eines Ölfilms zwischen Kolben bzw. Kolbenringen und Zylinderwand und damit zur Erhaltung der guten tribologische Eigenschaften genügend Poren vorhanden sind. Andererseits kann aber der absolute Ölverbrauch durch die sehr kleinen Poren (Hohlräume) gering gehalten werden. Im Gegensatz zu herkömmlichen Zylinderlaufflächenschichten, bei denen die Porosität nicht gezielt beeinflusst wurde bzw. werden konnte, weist die erfindungsgemässe Schicht somit eine poröse Grundstruktur auf, bei der die Grösse der einzelnen Poren innerhalb eines definierten Bereichs liegt. Durch die mechanische Nachbearbeitung werden die an der Oberfläche liegenden Poren geöffnet.The measures according to the invention ensure on the one hand that to absorb the oil to form an oil film between the piston or piston rings and cylinder wall and thus sufficient to maintain the good tribological properties Pores are present. On the other hand, the absolute oil consumption can the very small pores (cavities) are kept small. In contrast to conventional ones Cylinder tread layers in which the porosity is not specifically influenced was or could have been, the layer according to the invention thus has a porous one Basic structure, in which the size of the individual pores within a defined Range. The mechanical post-processing means that the Open pores on the surface.

In den beiliegenden Zeichnungen stellen dar:

  • Fig. 1 ein Diagramm, welches die Beziehung zwischen der gemittelten Rautiefe Ra und dem Leistungsniveau der Schichten wiedergibt.
  • Fig. 2 eine fotografischen Abbildung einer Zylinderlaufflächenschicht.
    • In the accompanying drawings:
  • Fig. 1 is a diagram showing the relationship between the average roughness depth R a and the performance level of the layers.
  • Fig. 2 is a photographic image of a cylinder tread layer.

    • Die Erfindung geht aus von der überraschenden Feststellung, dass zwischen der arithmetischen Mittenrauheit Ra und dem Verhalten der Schichten eine wichtige gegenseitige technische Beziehung besteht. In Fig. 1 ist in der Abszisse (x-Achse) die arithmetische Mittenrauheit Ra aufgetragen, in der Ordinate - qualitativ, nicht quantitativ-das Leistungsniveau L der Schichten. Das Leistungsniveau L ist das Integral von Reibungskoeffizient, Ölverbrauch und Verschleisswiderstand. Bei zu geringer arithmetischer Mittenrauheit Ra besteht die Gefahr eines adhäsiven Verschleisses, des sog. "Scuffing" (Gebiet A in Fig. 1). Bei zu grosser arithmetischer Mittenrauheit Ra steigt der Ölverbrauch in unannehmbarer Weise an (Gebiet B in Fig. 1). Die angestrebte Verbesserung ist durch die Kombination der im Kennzeichen des Anspruchs 1 genannten Merkmale erzielbar.The invention is based on the surprising finding that there is an important mutual technical relationship between the arithmetic mean roughness R a and the behavior of the layers. In Fig. 1, the arithmetic mean roughness R a is plotted in the abscissa (x-axis), the performance level L of the layers - qualitative, not quantitative - in the ordinate. The performance level L is the integral of the coefficient of friction, oil consumption and wear resistance. If the arithmetic mean roughness R a is too low , there is a risk of adhesive wear, so-called “scuffing” (area A in FIG. 1). If the arithmetic mean roughness R a is too great, the oil consumption increases in an unacceptable manner (region B in FIG. 1). The desired improvement can be achieved by combining the features mentioned in the characterizing part of claim 1.

    Anhand der fotografischen Abbildung einer Zylinderlaufflächenschicht von Fig. 2 werden nachstehend deren beispielsweiser Aufbau sowie ein bevorzugtes Verfahren zur Erzeugung derselben näher erläutert. Using the photographic illustration of a cylinder tread layer from FIG. 2 Below are their example structure and a preferred method to generate the same explained in more detail.

    Die mittels einer Plasmaspritzvorrichtung aufgebrachte Zylinderlaufflächenschicht 1 ist mit einer Vielzahl offener Poren 2, 3, 4 versehen. Die Poren weisen eine Grösse zwischen ca. 2 und 30 µm auf, wobei der überwiegende Teil zwischen ca. 5 und 20 µm gross ist. Der Porositäts-Grad der Schicht, d.h. der Anteil der Poren am gesamten Schichtvolumen, beträgt zwischen 1 und 5 %. Ebenso bewegt sich der flächenmässige Anteil der Poren 2, 3, 4 an der gesamten Oberfläche der Zylinderlaufflächenschicht 1 zwischen den genannten 1 und 5 %. Die Zylinderlaufflächenschicht 1 ist so aufgebaut, dass praktisch ausschliesslich Poren 2, 3, 4 mit einer Dimension <100 µm vorkommen.The cylinder tread layer applied by means of a plasma spraying device 1 is provided with a large number of open pores 2, 3, 4. The pores have a size between approx. 2 and 30 µm, the major part between approx. 5 and 20 µm is big. The degree of porosity of the layer, i.e. the proportion of pores in the total Shift volume, is between 1 and 5%. The areal movement also moves Proportion of pores 2, 3, 4 in the entire surface of cylinder surface layer 1 between the above 1 and 5%. The cylinder tread layer 1 is constructed that there are practically exclusively pores 2, 3, 4 with a dimension <100 µm.

    Die Zylinderlaufflächenschicht 1 weist einen Gehalt an gebundenem Sauerstoff von 0,5 bis 8 Gewichts-% auf, wobei der gebundene Sauerstoff mit Eisen FeO- und Fe3O4-Kristalle bildet, welche als Festschmierstoffe wirken. Vorzugsweise beträgt der Gehalt an Fe2O3 weniger als 0,2 Gewichts-%. Die Menge der gebildeten Oxyde kann durch Anreichern oder Reduzieren der während des Beschichtungsvorgangs durch die zu beschichtende Zylinderbohrung strömenden Luft mit Stickstoff oder Sauerstoff weiter beeinflusst werden. Der Anteil von in der Zylinderlaufflächenschicht 1 gebundenem Sauerstoff kann ausserdem durch die Geschwindigkeit der während des Beschichtungsvorgangs durch die zu beschichtende Zylinderbohrung strömenden Luft beeinflusst werden. Bei Ersatz der Luft durch reinen Sauerstoff wird der gebundene Anteil an Sauerstoff in der Schicht um einen Faktor von etwa zwei reduziert.The cylinder tread layer 1 has a bound oxygen content of 0.5 to 8% by weight, the bound oxygen forming FeO and Fe 3 O 4 crystals with iron, which act as solid lubricants. The Fe 2 O 3 content is preferably less than 0.2% by weight. The amount of oxides formed can be further influenced by enriching or reducing the air flowing through the cylinder bore to be coated with nitrogen or oxygen during the coating process. The proportion of oxygen bound in the cylinder tread layer 1 can also be influenced by the speed of the air flowing through the cylinder bore to be coated during the coating process. When the air is replaced by pure oxygen, the bound amount of oxygen in the layer is reduced by a factor of about two.

    Die vorwiegend aus Eisen bestehende Zylinderlaufflächenschicht 1 weist in etwa folgende chemische Zusammensetzung auf:

  • Fe = Differenz auf 100 Gewichts-%
  • C = 0,05 bis 1.5 Gewichts-%
  • Mn = 0,05 bis 3.5 Gewichts-%
  • Cr = 0.05 bis 18 Gewichts-%
  • Si = 0,01 bis 1 Gewichts-%
  • S = 0,001 bis 0,4 Gewichts-%
    • The cylinder running surface layer 1, which consists predominantly of iron, has approximately the following chemical composition:
  • Fe = difference to 100% by weight
  • C = 0.05 to 1.5% by weight
  • Mn = 0.05 to 3.5% by weight
  • Cr = 0.05 to 18% by weight
  • Si = 0.01 to 1% by weight
  • S = 0.001 to 0.4% by weight

    • Sie weist zweckmässig eine Mikrohärte nach Vickers HV0,3 von 350 bis 550 N/mm2 auf. It expediently has a micro hardness according to Vickers HV 0.3 of 350 to 550 N / mm 2 .

    Um eine gute Zerspanbarkeit der Zylinderlaufflächenschicht 1 durch Bildung von MnS-Verbindungen zu erreichen, enthält diese vorzugsweise zwischen 1,2 und 3,5 Gewichts-% Mangan und 0,05 bis 0,4 Gewichts-% Schwefel.To ensure good machinability of the cylinder tread layer 1 by forming To achieve MnS connections, it preferably contains between 1.2 and 3.5% by weight Manganese and 0.05 to 0.4% by weight sulfur.

    Die Poren 2, 3, 4 sind sowohl flächenmässig wie auch grössenmässig stochastisch in der Schicht verteilt. Zum Aufbringen der Schicht wird vorzugsweise eine rotierende Plasmaspritzvorrichtung verwendet wird, so dass der zu beschichtende Motorblock während des Beschichtungsvorgangs ruhen kann. Nach dem Beschichten wird die Zylinderlaufflächenschicht 1 mechanisch, insbesondere durch Honen, vorzugsweise Diamanthonen, nachbearbeitet bis die Rauheit der Zylinderlaufflächenschicht 1 auf eine arithmetische Mittenrauheit Ra von 0,02 bis 0,4 µm und eine gemittelte Rautiefe Rz von 0,5 bis 5 µm, vorzugsweise auf eine arithmetische Mittenrauheit Ra von 0,05 bis 0,2 µm und eine gemittelte Rautiefe Rz von 1 bis 3 µm eingestellt, eingestellt ist.The pores 2, 3, 4 are distributed stochastically in terms of area as well as size. A rotating plasma spray device is preferably used to apply the layer, so that the engine block to be coated can rest during the coating process. After coating, the cylinder tread layer 1 is reworked mechanically, in particular by honing, preferably diamond honing, until the roughness of the cylinder tread layer 1 has an arithmetic mean roughness R a of 0.02 to 0.4 μm and an average roughness depth R z of 0.5 to 5 µm, preferably set to an arithmetic mean roughness R a of 0.05 to 0.2 µm and an average roughness depth R z of 1 to 3 µm.

    Der Anteil der Poren 2, 3, 4 am gesamten Schichtvolumen (Porositäts-Grad), wie auch die Grösse (Dimension) der Poren 2, 3, 4 kann durch Ändern der Beschichtungsparameter sowie der Partikelgrösse des Beschichtungspulvers gezielt beeinflusst werden. Dabei spielt insbesondere die Enthalpie des Plasmas eine massgebende Rolle, welche vorwiegend durch den Wasserstoffgehalt im Plasmagas sowie den Plasmastrom bestimmt wird.The proportion of pores 2, 3, 4 in the total layer volume (degree of porosity), such as The size (dimension) of the pores 2, 3, 4 can also be changed by changing the coating parameters and the particle size of the coating powder can be influenced in a targeted manner. The enthalpy of the plasma plays a decisive role here, which is mainly due to the hydrogen content in the plasma gas and the plasma flow is determined.

    Beim erfindungsgemässen Verfahren zur Herstellung einer Zylinderlaufflächenschicht nach dem Anspruch 1, wird die Zylinderlaufflächenschicht 1 durch Plasmaspritzen eines gas- oder wasserverdüsten Beschichtungspulvers mit einer Partikelgrösse zwischen 5 und 100 µm, vorzugsweise von 10 und 50 µm, erzeugt, wobei der Spritzabstand, d.i. der Abstand zwischen dem Pulverinjektor des Plasmaspritzgerätes und der zu beschichtenden Oberfläche, 20 bis 50 mm beträgt.In the method according to the invention for producing a cylinder running surface layer according to claim 1, the cylinder tread layer 1 by plasma spraying a gas or water atomized coating powder with a particle size between 5 and 100 microns, preferably from 10 and 50 microns, the Spraying distance, i.e. the distance between the powder injector of the plasma spraying device and the surface to be coated is 20 to 50 mm.

    Als Plasmagas wird zweckmässig Argon mit einem Anteil von 0,5 bis 5 NLPM (Normal Liter pro Minute) Wasserstoff verwendet. Der Plasmastrom liegt zweckmässig zwischen 100 und 500 Ampere, vorzugsweise zwischen 260 und 360 Ampere, bei einer Spannung von zwischen 35 und 45 Volt. Argon with a proportion of 0.5 to 5 NLPM is expediently used as the plasma gas (Normal liters per minute) uses hydrogen. The plasma flow is convenient between 100 and 500 amps, preferably between 260 and 360 amps, at one Voltage between 35 and 45 volts.

    Eine solche Zylinderlaufflächenschicht 1 eignet sich insbesondere zum Aufbringen auf Substrate aus Al-Gusslegierungen, Al-Knetlegierungen, Gusseisen mit Lamellengraphit, Gusseisen mit Vermikulargraphit, Gusseisen mit Kugelgraphit oder Magnesium-Gusslegierungen.Such a cylinder tread layer 1 is particularly suitable for application on substrates made of cast aluminum alloys, wrought aluminum alloys, cast iron with lamellar graphite, Cast iron with vermicular graphite, cast iron with spheroidal graphite or magnesium casting alloys.

    Claims (21)

    Zylinderlaufflächenschicht für Hubkolbenmotoren, gekennzeichnet durch die Kombination folgender Merkmale: die Zylinderlaufflächenschicht (1) ist durch Plasmaspritzen aufgebracht; die Zylinderlaufflächenschicht-Oberfläche weist eine Vielzahl von offenen Poren (2, 3, 4) auf; der Porositäts-Grad der Zylinderlaufflächenschicht-Oberfläche liegt zwischen 0,5 und 10 %; die statistisch mittlere Porengrösse liegt zwischen 1 und 50 µm, wobei zum Mindesten annähernd ausschliesslich Poren <100 µm vorhanden sind; die Poren (2, 3, 4) sind in der Zylinderlaufflächenschicht-Oberfläche sowohl flächenmässig wie auch grössenmässig stochastisch verteilt; die Zylinderlaufflächenschicht (1) weist einen Gehalt an gebundenem Sauerstoff von 0,5 bis 8 Gewichts-% auf; die Zylinderlaufflächenschicht (1) weist eingelagerte FeO- und Fe3O4-Kristalle zur Bildung von Festschmierstoffen auf; und die Rauheit der Zylinderlaufflächenschicht (1) ist durch mechanische Nachbearbeitung auf eine arithmetische Mittenrauheit Ra von 0,02 bis 0,4 µm und eine gemittelte Rautiefe Rz von 0,5 bis 5 µm eingestellt. Cylinder surface layer for reciprocating engines, characterized by the combination of the following features: the cylinder tread layer (1) is applied by plasma spraying; the cylinder tread layer surface has a multiplicity of open pores (2, 3, 4); the degree of porosity of the cylinder tread layer surface is between 0.5 and 10%; the statistically mean pore size is between 1 and 50 µm, with at least almost exclusively pores <100 µm; the pores (2, 3, 4) are distributed stochastically in terms of area and size in the surface of the cylinder tread layer; the cylinder tread layer (1) has a bound oxygen content of 0.5 to 8% by weight; the cylinder running surface layer (1) has embedded FeO and Fe 3 O 4 crystals to form solid lubricants; and the roughness of the cylinder tread layer (1) is adjusted by mechanical finishing to an arithmetic mean roughness R a of 0.02 to 0.4 µm and an average roughness depth R z of 0.5 to 5 µm. Zylinderlaufflächenschicht nach Anspruch 1, dadurch gekennzeichnet, dass die statistisch mittlere Porengrösse zwischen 1 und 10 µm und der Porositäts-Grad zwischen 0,5 und 5 % liegt.Cylinder tread layer according to claim 1, characterized in that the statistically mean pore size is between 1 and 10 µm and the degree of porosity is between 0.5 and 5%. Zylinderlaufflächenschicht nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Rauheit der Zylinderlaufflächenschicht (1) auf eine arithmetische Mittenrauheit Ra von 0,05 bis 0,2 µm und eine gemittelte Rautiefe Rz von 1 bis 3 µm eingestellt ist.Cylinder tread layer according to claim 1 or 2, characterized in that the roughness of the cylinder tread layer (1) is set to an arithmetic mean roughness R a of 0.05 to 0.2 µm and an average roughness depth R z of 1 to 3 µm. Zylinderlaufflächenschicht nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Rauheit durch Nachbearbeitung mittels Honen eingestellt ist. Cylinder tread layer according to one of claims 1 to 3, characterized in that the roughness is set by finishing by honing. Zylinderlaufflächenschicht nach Anspruch 4, dadurch gekennzeichnet, dass die Rauheit durch Nachbearbeitung mittels Diamanthonen eingestellt ist.Cylinder tread layer according to claim 4, characterized in that the roughness is adjusted by post-processing by means of diamond honing. Zylinderlaufflächenschicht nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Zylinderlaufflächenschicht eine Vickers-Mikrohärte HV0,3 von 350 bis 550 N/mm2 aufweist.Cylinder tread layer according to one of claims 1 to 5, characterized in that the cylinder tread layer has a Vickers microhardness HV 0.3 of 350 to 550 N / mm 2 . Zylinderlaufflächenschicht nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Zylinderlaufflächenschicht (1) zusätzlich C, Mn, Cr, Si und S enthält.Cylinder tread layer according to one of claims 1 to 6, characterized in that the cylinder tread layer (1) additionally contains C, Mn, Cr, Si and S. Zylinderlaufflächenschicht nach Anspruch 7, dadurch gekennzeichnet, dass die Zylinderlaufflächenschicht (1) folgende chemische Zusammensetzung aufweist: Fe = Differenz auf 100 Gewichts-% C = 0,05 bis 1.5 Gewichts-% Mn = 0,05 bis 3.5 Gewichts-% Cr = 0.05 bis 18 Gewichts-% Si = 0,01 bis 1 Gewichts-% S = 0,001 bis 0,4 Gewichts-%. Cylinder tread layer according to claim 7, characterized in that the cylinder tread layer (1) has the following chemical composition: Fe = difference to 100% by weight C = 0.05 to 1.5% by weight Mn = 0.05 to 3.5% by weight Cr = 0.05 to 18% by weight Si = 0.01 to 1% by weight S = 0.001 to 0.4% by weight. Zylinderlaufflächenschicht nach Anspruch 7, dadurch gekennzeichnet, dass die Zylinderlaufflächenschicht (1) folgende chemische Zusammensetzung aufweist: Fe = Differenz auf 100 Gewichts-% C = 0,05 bis 0.8 Gewichts-% Mn = 0,05 bis 1.8 Gewichts-% Cr = 11.5 bis 18 Gewichts-% Si = 0,01 bis 1 Gewichts-% S = 0,002 bis 0,2 Gewichts-%. Cylinder tread layer according to claim 7, characterized in that the cylinder tread layer (1) has the following chemical composition: Fe = difference to 100% by weight C = 0.05 to 0.8% by weight Mn = 0.05 to 1.8% by weight Cr = 11.5 to 18% by weight Si = 0.01 to 1% by weight S = 0.002 to 0.2% by weight. Zylinderlaufflächenschicht nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Zylinderlaufflächenschicht (1) zur Verbesserung der Zerspanbarkeit zwischen 1,2 und 3,5 Gewichts-% Mn und 0,05 bis 0,4 Gewichts-% S enthält.Cylinder tread layer according to one of claims 1 to 6, characterized in that the cylinder tread layer (1) contains between 1.2 and 3.5% by weight Mn and 0.05 to 0.4% by weight S to improve machinability. Verfahren zur Herstellung einer Zylinderlaufflächenschicht nach dem Anspruch 1, dadurch gekennzeichnet, dass die Zylinderlaufflächenschicht (1) durch Plasmaspritzen eines gas- oder wasserverdüsten Beschichtungspulvers mit einer Partikelgrösse zwischen 5 und 100 µm erzeugt wird, wobei der Spritzabstand 20 bis 50 mm beträgt.A method for producing a cylinder tread layer according to claim 1, characterized in that the cylinder tread layer (1) is produced by plasma spraying a gas- or water-atomized coating powder with a particle size between 5 and 100 µm, the spraying distance being 20 to 50 mm. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass das Beschichtungspulver eine Partikelgrösse zwischen 10 und 50 µm aufweist.A method according to claim 11, characterized in that the coating powder has a particle size between 10 and 50 microns. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass das Beschichtungspulver folgende chemische Zusammensetzung aufweist: Fe = Differenz auf 100 Gewichts-% C = 0,05 bis 1.5 Gewichts-% Mn = 0,05 bis 3.5 Gewichts-% Cr = 0.05 bis 18 Gewichts-% Si = 0,01 bis 1 Gewichts-% S = 0,001 bis 0,4 Gewichts-%. A method according to claim 11 or 12, characterized in that the coating powder has the following chemical composition: Fe = difference to 100% by weight C = 0.05 to 1.5% by weight Mn = 0.05 to 3.5% by weight Cr = 0.05 to 18% by weight Si = 0.01 to 1% by weight S = 0.001 to 0.4% by weight. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass das Beschichtungspulver folgende chemische Zusammensetzung aufweist: Fe = Differenz auf 100 Gewichts-% C = 0,05 bis 0.8 Gewichts-% Mn = 0,05 bis 1.8 Gewichts-% Cr = 11.5 bis 18 Gewichts-% Si = 0,01 bis 1 Gewichts-% S = 0,002 bis 0,2 Gewichts-%. A method according to claim 11 or 12, characterized in that the coating powder has the following chemical composition: Fe = difference to 100% by weight C = 0.05 to 0.8% by weight Mn = 0.05 to 1.8% by weight Cr = 11.5 to 18% by weight Si = 0.01 to 1% by weight S = 0.002 to 0.2% by weight. Verfahren nach einem der Ansprüch 11 bis 14, dadurch gekennzeichnet, dass die mechanische Nachbehandlung der Zylinderlaufflächenschicht (1) durch Diamanthonen erfolgt.Method according to one of claims 11 to 14, characterized in that the mechanical aftertreatment of the cylinder tread layer (1) is carried out by diamond honing. Verfahren nach einem der Ansprüche 11 bis 15, dadurch gekennzeichnet, dass zur Erzeugung der gewünschten Schichteigenschaften bzw. zum Verändern der Porengrösse und/oder des Porositäts-Grads die Grösse der Beschichtungspartikel und/oder die chemische Zusammensetzung des Beschichtungsmaterials und/oder die Enthalpie des Plasmas variiert wird/werden.Method according to one of claims 11 to 15, characterized in that to generate the desired layer properties or to change the pore size and / or the degree of porosity, the size of the coating particles and / or the chemical composition of the coating material and / or the enthalpy of the plasma will be varied. Verfahren nach Anspruch 16, dadurch gekennzeichnet, dass die Enthalpie des Plasmas durch Ändern des Plasmastroms und/oder des Anteils an Wasserstoff im Plasmagas variiert wird.A method according to claim 16, characterized in that the enthalpy of the plasma is varied by changing the plasma flow and / or the proportion of hydrogen in the plasma gas. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass die Enthalpie des Plasmas durch Ändern des Plasmastroms variiert wird, wobei der Plasmastrom zwischen 100 und 500 Ampere gehalten wird.A method according to claim 17, characterized in that the enthalpy of the plasma is varied by changing the plasma current, the plasma current being kept between 100 and 500 amperes. Verfahren nach Anspruch 18, dadurch gekennzeichnet, dass der Plasmastrom zwischen 260 und 360 Ampere gehalten wirdA method according to claim 18, characterized in that the plasma current is kept between 260 and 360 amps Verfahren nach einem der Ansprüche 11 bis 19, dadurch gekennzeichnet, dass der Plasmaspritzvorrichtung ein Plasmagas mit einem Anteil von 0,5 bis 5 NLPM (Normal-Liter pro Minute) Wasserstoff zugeführt wird.Method according to one of claims 11 to 19, characterized in that the plasma spray device is supplied with a plasma gas with a proportion of 0.5 to 5 NLPM (normal liters per minute) of hydrogen. Verfahren nach Anspruch 20, dadurch gekennzeichnet, dass als Plasmagas Argon eingesetzt wird.A method according to claim 20, characterized in that argon is used as the plasma gas.
    EP03405004A 2002-02-27 2003-01-07 Coated running surfaces of combustion-engine cylinders and process of its manufacture Expired - Lifetime EP1340834B1 (en)

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    WO2011044979A1 (en) * 2009-10-14 2011-04-21 Bayerische Motoren Werke Aktiengesellschaft Internal combustion engine having a crankcase and method for producing a crankcase
    DE102009049323A1 (en) * 2009-10-14 2011-06-01 Bayerische Motoren Werke Aktiengesellschaft Internal combustion engine with a crankcase and method for producing a crankcase
    US10145331B2 (en) 2009-10-14 2018-12-04 Bayerische Motoren Werke Aktiengesellschaft Internal combustion engine having a crankcase and method for producing a crankcase
    DE102009049323B4 (en) * 2009-10-14 2011-11-10 Bayerische Motoren Werke Aktiengesellschaft Internal combustion engine with a crankcase and method for producing a crankcase
    US8492318B2 (en) 2009-12-03 2013-07-23 Sulzer Metco Ag Spray material, a thermal spray layer, as well as a cylinder with a thermal spray layer
    AU2010246513B2 (en) * 2009-12-03 2014-07-24 Sulzer Metco Ag Spray material, a thermal spray layer, as well as a cylinder with a thermal spray layer
    EP2330228A1 (en) 2009-12-03 2011-06-08 Sulzer Metco AG Spray material, thermal spray layer and cylinder with a thermal spray layer
    WO2011147526A1 (en) * 2010-05-22 2011-12-01 Daimler Ag Wire-like spray material, functional layer which can be produced therewith and process for coating a substrate with a spray material
    US9487660B2 (en) 2010-05-22 2016-11-08 Daimler Ag Wire-like spray material, functional layer which can be produced therewith and process for coating a substrate with a spray material
    CN110093578A (en) * 2013-07-09 2019-08-06 日产自动车株式会社 Iron series spray coating, valve device with cylinder stop mechanism of ic engine and internal combustion engine sliding equipment
    WO2015074775A1 (en) * 2013-11-20 2015-05-28 Ks Aluminium-Technologie Gmbh Method for producing a sprayed cylinder running surface of a cylinder crankcase of an internal combustion engine and such a cylinder crankcase
    RU2647064C2 (en) * 2013-11-20 2018-03-13 Кс Хуаюй Алутек Гмбх Method for producing a sprayed cylinder running surface of a cylinder crankcase of an internal combustion engine and such a cylinder crankcase
    WO2017137500A1 (en) 2016-02-12 2017-08-17 Oerlikon Surface Solutions Ag, Päffikon Tribological system of an internal combustion engine with a coating
    US10677355B2 (en) 2016-02-12 2020-06-09 Oerlikon Surface Solutions Ag, Pfäffikon Tribological system of an internal combustion engine with a coating

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    JP2003253418A (en) 2003-09-10
    ATE429524T1 (en) 2009-05-15
    CN100338253C (en) 2007-09-19
    CA2416692C (en) 2006-05-02
    CN1441078A (en) 2003-09-10
    KR20030071507A (en) 2003-09-03
    US6701882B2 (en) 2004-03-09
    CA2416692A1 (en) 2003-08-27
    CH695339A5 (en) 2006-04-13
    EP1340834B1 (en) 2009-04-22
    KR100593341B1 (en) 2006-06-26
    EP1340834A3 (en) 2004-03-31
    US20030164150A1 (en) 2003-09-04
    DE50311438D1 (en) 2009-06-04

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