EP3485056B1 - Coating of cylindrical boreholes without previous activation of the coating - Google Patents

Coating of cylindrical boreholes without previous activation of the coating Download PDF

Info

Publication number
EP3485056B1
EP3485056B1 EP17739279.2A EP17739279A EP3485056B1 EP 3485056 B1 EP3485056 B1 EP 3485056B1 EP 17739279 A EP17739279 A EP 17739279A EP 3485056 B1 EP3485056 B1 EP 3485056B1
Authority
EP
European Patent Office
Prior art keywords
layer
boundary surface
base material
bore
functional layer
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.)
Active
Application number
EP17739279.2A
Other languages
German (de)
French (fr)
Other versions
EP3485056A1 (en
Inventor
Flavio VOLPE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oerlikon Metco AG
Original Assignee
Oerlikon Metco AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oerlikon Metco AG filed Critical Oerlikon Metco AG
Publication of EP3485056A1 publication Critical patent/EP3485056A1/en
Application granted granted Critical
Publication of EP3485056B1 publication Critical patent/EP3485056B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • C23C28/02—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 only including layers of metallic material
    • C23C28/021—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 only including layers of metallic material including at least one metal alloy 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
    • C23C28/02—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 only including layers of metallic material
    • C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
    • 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
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • 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
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/004—Cylinder liners
    • 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
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/18—Other cylinders

Definitions

  • the cylinder bores of some piston internal combustion engines are provided with a coating, usually by means of thermal spraying, in order to minimize weight and / or friction and / or wear. This reduces fuel and oil consumption and preferably also makes the surface of the cylinder bore more corrosion-resistant.
  • the US4044217 A discloses a cylinder of a reciprocating internal combustion engine, the cylinder comprising a bore with an inner jacket which is formed from a base material, the base material being at least partially provided with a layer system in the region of the bore.
  • the adhesion of this layer to the cylinder material is problematic so that the layer runs the risk of flaking off during operation.
  • the surface of the cylinder bore is usually roughened (activated). Such an activation ensures that a mechanical interlocking is established between the layer and the base material of the cylinder block, i.e. that there is a form fit. This preprocessing step of activating the cylinder surface increases the cost of the coating.
  • the entanglement achieved by the activation between the layer and the base material of the cylinder block improves the adhesion of the layer to the base material and contributes to a long service life of the cylinder.
  • Various techniques can be used to carry out the activation.
  • the surface can be roughened by means of corundum blasting, by means of a laser, by means of a high pressure water jet and / or by means of a low pressure water jet.
  • Another possibility for activation consists in providing the surface with a profile with undercuts, for example by means of machining.
  • the dovetail geometry is used to advantage here.
  • Figure 1 Shows accordingly Figure 1 the mechanical entanglement of the spray coating 3 with the base material 1 by activating the base material before coating. According to the prior art, this improves the adhesion to the base material 1, for example a cylinder bore.
  • the present invention is therefore based on the object of specifying a method that allows the thermally sprayed layer to be applied to the jacket of a cylinder bore in an adhesive manner without the need for activation, in particular mechanical activation, of the surface to be coated.
  • the cylinder comprises at least one bore with an inner jacket which is formed from a base material, the base material being at least partially provided with a layer system in the region of the bore.
  • a first interface is formed between the base material and the layer system, the first interface, apart from the surface roughness resulting from the production of the bore, not including any profiling applied to activate the surface, in particular no profiling applied to mechanically activate the surface.
  • the layer system comprises at least one thermally sprayed layer, in particular a thermally sprayed layer by means of plasma spraying, preferably a layer thermally sprayed by means of a rotating plasma torch, and the thermally sprayed layer at least partially forms the jacket surface of the bore and can act there as a functional layer.
  • the functional layer can preferably also be understood as a functional layer, particularly preferably also as a thermally sprayed functional layer.
  • the core of the process is the application of an adhesive layer directly to the base material of the cylinder casing, the adhesive layer entering into a chemical bond at least with the base material.
  • the adhesive layer can comprise the interface material, in particular consist of the interface material.
  • the adhesive layer can be built up from the interface material.
  • the interface material comprises molybdenum (Mo) and at least one further element, but can in particular also essentially consist of molybdenum and at least one further element; in particular, the interface material can consist of molybdenum and at least one further element. If the presence of a further element is mentioned in the present description or in the claims, this can, but does not have to be, present in elemental form, but can also be present as a molecule and / or within a chemical compound.
  • the proportion of molybdenum in the interface material, in particular in the adhesive layer can be in a range from 30 to 90% by weight and the The proportion of the further element in the interface material, in particular in the adhesive layer, is in a range from 70 to 10% by weight, preferably the proportion of molybdenum in the interface material in a range from 40 to 80% by weight and the proportion of the further element in the Interface material lie in a range from 60 to 20% by weight, particularly preferably the proportion of molybdenum in the interface material in a range from 50 to 70% by weight and the proportion of the further element in the interface material in a range from 50 to 30% by weight. -% lie.
  • the proportion of molybdenum in the interface material can be in a range from 55 to 65% by weight or from 58 to 62% by weight or at 60% by weight and the proportion of the further element in the interface material in a range from 45% to 35% by weight or from 42 to 38% by weight or at 40% by weight.
  • the interface material can also contain a proportion of impurities, for example S and P, in the range from 0.01 to 0.2% by weight, preferably 0.01 to 0.1% by weight.
  • the particle size of the powder of the further element and / or the functional layer can be in the range from 5 to 25 ⁇ m or 10 to 45 ⁇ m or 15 to 60 ⁇ m.
  • an adhesive layer does not necessarily have to be formed with a well-defined interface to the other layer or layers of the layer system, unless otherwise defined. For example, this can merge into another layer via a composition gradient, or a well-defined layer can be missing due to interface profiling.
  • the material of the adhesive layer is also selected such that this material also forms a chemical bond with the material of the thermally sprayed functional layer to be applied and thus adheres.
  • the adhesive layer is designed in such a way that it has a porosity and / or columnarity which leads to the thermally sprayed functional layer to be applied adhering sufficiently at least mechanically to the adhesive layer. For example, this can be achieved through targeted columnar growth. It is also possible to achieve this by means of increased porosity.
  • Figure 2 shows an embodiment according to the invention, according to which the adhesion of the sprayed functional layer 3 to the base material 1 is ensured without activating the surface of the base material 1 by chemical bonding between the adhesive layer 5 and the base material 1 and by mechanical and / or chemical bonding between the adhesive layer 5 and the functional layer 3 is.
  • the coating of the cylinder bore in particular the layer system
  • the coating of the cylinder bore can be designed in the form of a gradual transition and / or a gradient, in particular in terms of the chemical composition and / or the structural structure.
  • a gradual layer in particular a gradual layer system, can therefore be understood to mean that the gradual layer then directly at the first interface comprises material which forms a chemical bond with the surface of the base material of the cylinder, i.e. in particular the material of the adhesive layer, i.e. the Interface material.
  • the layer material With increasing distance from this surface, i.e. with increasing layer thickness, the layer material then gradually changes into the layer material of the protective thermally sprayed layer that is actually to be applied, preferably the functional layer.
  • the gradual layer in particular the gradual layer system, with the gradually changing composition, that is to say the gradual transition and / or the gradient, can comprise the following two variants:
  • the interface material gradually changes into the material of the functional layer, in particular into the functional layer, where: Start of the layer with the gradually changing composition at the first interface with 0% by weight of material of the functional layer and 100% by weight of interface material, whereby the interface material can comprise 60% by weight of molybdenum and 40% by weight of further element, preferably the interface material can consist of 60% by weight molybdenum and 40% by weight Ni5Al. End of the layer with the gradually changing composition with 100% by weight of functional layer and 0% by weight of interface material, so that the end of the gradual layer at least partially forms the outer surface of the bore of the cylinder and can act there as a functional layer.
  • the interface material can comprise molybdenum and the further element, in particular consist of this, wherein the further element can preferably correspond to the material of the functional layer, and the interface material gradually merges into the material of the functional layer, in particular the adhesive layer merges into the functional layer, where: Start of the layer with the gradually changing composition at the first interface with 40% by weight of additional element and 50 to 70% by weight, preferably 60% by weight of molybdenum.
  • variant 2 can then have the following chemical composition and the following course:
  • the proportion of the interface material in the gradual layer with the gradually changing composition from the start to the end can preferably decrease linearly or exponentially, in particular in variant 1 and / or variant 2, and / or the proportion of the functional layer in the
  • the layer with the gradually changing composition can preferably increase linearly or exponentially from start to finish, in particular in the case of variant 1 and / or variant 2.
  • the coating of the cylinder bore is designed in the form of a gradient.
  • the layer to be applied then comprises materials which enter into a chemical bond with the surface of the base material of the cylinder, that is to say in particular the material of the adhesive layer.
  • the layer material With increasing distance from this surface, i.e. with increasing layer thickness, the layer material then gradually merges into the layer material of the protective thermally sprayed layer that is actually to be applied.
  • This could be implemented, for example, via a double injection with the injection of the adhesive layer decreasing over time and / or the injection of the functional layer increasing over time. In this way, there is actually only one layer with a gradually changing composition and / or morphology, that is to say a gradual layer, in particular a gradual layer system.
  • the layer with the gradually changing composition ie the gradual transition, ie a grading layer
  • the layer with the gradually changing composition can also be implemented by a single injection, with two separate feeds for the
  • the material of the adhesive layer and the functional layer can be used, in particular two powder feeders which are brought together in a Y-shaped component.
  • a material composition can be specified which comprises NiAl and Mo.
  • the interface material can comprise molybdenum and Ni5Al, preferably consist of molybdenum and Ni5Al.
  • Table 1 shows the average tensile strengths achieved with conventional, known activation (mechanical, corundum) and with an interface material consisting of molybdenum and Ni5Al, in particular the interface material can also consist of molybdenum and Ni5Al and a proportion of impurities in the range from 0.1 to 0.3 wt. -% exist.
  • Table 1 Comparison of the adhesive tensile strengths with conventionally known activation and with an interface material consisting of molybdenum and Ni5Al.
  • Proportion of molybdenum in the adhesive layer [% by weight] Proportion of Ni5AI in the adhesive layer [% by weight] Type of activation / adhesive layer Average adhesive tensile strength [Mpa] None None Activated with corundum 18.1 None None Mechanically activated 35.2 30th 70 Adhesive layer 40.8 40 60 Adhesive layer 41.5 60 40 Adhesive layer 44.0 70 30th Adhesive layer 41.0 90 10 Adhesive layer 30.0
  • the example relates to the invention according to the first embodiment.
  • the bore of a cylinder is coated, the base material of the cylinder being an aluminum alloy and the bore having a diameter of 85 mm and the bore 170 mm deep.
  • This hole is to be coated with a thermally sprayed iron-based layer (95% Fe, 1.5% Cr, 1% Mn, 1% C) that is 200-300 micrometers thick.
  • Atmospheric plasma spraying (APS) should be used as the coating method for thermal spraying.
  • powdery coating material is continuously melted in a plasma, atomized in liquid form and then applied to the inside of the base material of the cylinder wall, where it solidifies and forms a closed layer.
  • the plasma torch rotates during the melting process so that the inside of the cylinder wall is evenly coated with a layer.
  • a 5-150 micrometer thick adhesive layer made of a mixture of molybdenum and nickel-aluminum powder is applied directly to the base material.
  • This material has the advantage that it forms chemical bonds both with the base material and with the actual layer material. Chemical compounds of an ionic nature, for example, arise at the interface with the base material, and ionic bonds and, in addition, mechanical entanglement due to the rough spray coating, also arise at the interface between the adhesive layer and the layer material. This ensures adequate adhesion at both interfaces.

Landscapes

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

Description

Die Zylinderbohrungen einiger Kolben-Verbrennungsmotoren werden mit einer Beschichtung in der Regel mittels thermischem Spritzen versehen um das Gewicht und/oder die Reibung und/oder den Verschleiss zu minimieren. Hierdurch wird der Treibstoff- und Ölverbrauch reduziert und vorzugsweise auch die Oberfläche der Zylinderbohrung korrosionsbeständiger gemacht. Die US4044217 A offenbart einen Zylinder eines Kolben-Verbrennungsmotors, wobei der Zylinder eine Bohrung mit einem innerem Mantel der aus einem Grundmaterial gebildet wird umfasst, wobei im Bereich der Bohrung das Grundmaterial zumindest teilweise mit einem Schichtsystem versehen ist.The cylinder bores of some piston internal combustion engines are provided with a coating, usually by means of thermal spraying, in order to minimize weight and / or friction and / or wear. This reduces fuel and oil consumption and preferably also makes the surface of the cylinder bore more corrosion-resistant. the US4044217 A discloses a cylinder of a reciprocating internal combustion engine, the cylinder comprising a bore with an inner jacket which is formed from a base material, the base material being at least partially provided with a layer system in the region of the bore.

Allerdings ist die Haftung dieser Schicht auf dem Zylindermaterial problematisch so dass die Schicht im Betrieb Gefahr läuft abzuplatzen. Um diese auf das für die Anwendung notwendige Mass zu erhöhen wird die Oberfläche der Zylinderbohrung in der Regel aufgeraut (aktiviert). Eine solche Aktivierung stellt sicher, dass eine mechanische Verhakung zwischen Schicht und Grundmaterial des Zylinderblocks hergestellt wird, d.h. es zum Formschluss kommt. Dieser Vorbearbeitungsschritt der Aktivierung der Zylinderlauffläche erhöht die Kosten der Beschichtung.However, the adhesion of this layer to the cylinder material is problematic so that the layer runs the risk of flaking off during operation. In order to increase this to the extent necessary for the application, the surface of the cylinder bore is usually roughened (activated). Such an activation ensures that a mechanical interlocking is established between the layer and the base material of the cylinder block, i.e. that there is a form fit. This preprocessing step of activating the cylinder surface increases the cost of the coating.

Die durch die Aktivierung erreichte Verschränkung zwischen Schicht und Grundmaterial des Zylinderblocks verbessert die Haftung der Schicht auf dem Grundmaterial und trägt zu einer langen Lebensdauer des Zylinders bei. Um die Aktivierung durchzuführen können unterschiedliche Techniken angewandt werden. Beispielsweise kann die Oberfläche mittels Korundstrahlen, mittels Laser, mittels einem Hochdruckwasserstrahl und/oder mittels einem Niederdruckwasserstrahl aufgeraut werden. Eine weitere Möglichkeit der Aktivierung besteht darin, die Oberfläche mit einer Profilierung mit Hinterschnitten beispielsweise mittels spanabhebender Bearbeitung zu versehen. Beispielsweise kommt hier die Schwalbenschwanzgeometrie mit Vorteil zum Einsatz.The entanglement achieved by the activation between the layer and the base material of the cylinder block improves the adhesion of the layer to the base material and contributes to a long service life of the cylinder. Various techniques can be used to carry out the activation. For example, the surface can be roughened by means of corundum blasting, by means of a laser, by means of a high pressure water jet and / or by means of a low pressure water jet. Another possibility for activation consists in providing the surface with a profile with undercuts, for example by means of machining. For example, the dovetail geometry is used to advantage here.

Entsprechend zeigt Figur 1 die mechanische Verhakung der Spritzschicht 3 mit dem Grundmaterial 1 durch Aktivierung des Grundmaterials vor dem Beschichten. Dadurch wird gemäss Stand der Technik die Haftung auf dem Grundmaterial 1 beispielsweise einer Zylinderbohrung verbessert.Shows accordingly Figure 1 the mechanical entanglement of the spray coating 3 with the base material 1 by activating the base material before coating. According to the prior art, this improves the adhesion to the base material 1, for example a cylinder bore.

Die oben beschriebenen Aktivierungsverfahren haben unter anderem den Nachteil dass sie lediglich mit erhöhtem Produktionsaufwand realisierbar sind. Neben der für den Zusatzschritt benötigten erhöhten Prozessdauer kommen auch noch zusätzliche Investitionskosten für das die Aktivierung durchführende Werkzeug und/oder die Maschine hinzu.The activation processes described above have, among other things, the disadvantage that they can only be implemented with increased production outlay. In addition to the increased process time required for the additional step, there are also additional investment costs for the tool and / or the machine performing the activation.

Es gab bereits frühe Versuche, die Oberflächenaktivierung mittels einer Zwischenschicht vermeiden zu können. Beispielsweise offenbart Shepard in US 2588422 eine Molybdänschicht als Zwischenschicht. Diese bildet dann einerseits mit dem Grundmaterial und andererseits mit der gespritzten funktionalen Schicht jeweils eine Grenzfläche. Abgesehen davon, dass elementares Molybdän ein sehr weiches Material ist, ist bei diesem Ansatz auch noch die Problematik vorhanden, dass es in nicht befriedigender Art und Weise möglich ist, die Haftung an beiden Grenzflächen in notwendiger Weise zu verbessern.There have been early attempts to avoid surface activation by means of an intermediate layer. For example, Shepard discloses in US 2588422 a molybdenum layer as an intermediate layer. This then forms an interface on the one hand with the base material and on the other hand with the sprayed functional layer. Apart from the fact that elemental molybdenum is a very soft material, there is also the problem with this approach that it is not possible in a satisfactory manner to necessarily improve the adhesion at both interfaces.

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren anzugeben das erlaubt die thermisch gespritzte Schicht auf den Mantel einer Zylinderbohrung haftend aufzubringen ohne dass hierfür eine Aktivierung, insbesondere eine mechanische Aktivierung, der zu beschichtenden Oberfläche notwendig wäre.The present invention is therefore based on the object of specifying a method that allows the thermally sprayed layer to be applied to the jacket of a cylinder bore in an adhesive manner without the need for activation, in particular mechanical activation, of the surface to be coated.

Erfindungsgemäss wird die Aufgabe durch den erfindungsgemässen Zylinder nach Ansprüchen 1 und dem erfindungsgemässen Verfahren nach Anspruch 8 gelöst. Ansprüche 2 bis 7 und 9 bis 11 beziehen sich auf weitere vorteilhafte Ausgestaltungen der vorliegenden Erfindung und Ansprüche 12 und 13 beziehen sich auf den entsprechenden Motor beziehungsweise dessen Herstellung.According to the invention, the object is achieved by the cylinder according to the invention according to claims 1 and the method according to the invention according to claim 8. Claims 2 to 7 and 9 to 11 relate to further advantageous embodiments of the present invention and claims 12 and 13 relate to the corresponding motor or its manufacture.

Der Zylinder umfasst zumindest eine Bohrung mit innerem Mantel der aus einem Grundmaterial gebildet wird, wobei im Bereich der Bohrung das Grundmaterial zumindest teilweise mit einem Schichtsystem versehen ist. Dabei wird zwischen dem Grundmaterial und Schichtsystem eine erste Grenzfläche gebildet, wobei die erste Grenzfläche abgesehen von der durch die Herstellung der Bohrung entstandene Oberflächenrauigkeit keine zur Aktivierung der Oberfläche angebrachte Profilierung umfasst, insbesondere keine zur mechanischen Aktivierung der Oberfläche angebrachte Profilierung umfasst.The cylinder comprises at least one bore with an inner jacket which is formed from a base material, the base material being at least partially provided with a layer system in the region of the bore. A first interface is formed between the base material and the layer system, the first interface, apart from the surface roughness resulting from the production of the bore, not including any profiling applied to activate the surface, in particular no profiling applied to mechanically activate the surface.

Das Schichtsystem umfasst zumindest eine thermisch gespritzte Schicht, insbesondere eine mittels Plasmaspritzen thermisch gespritzte Schicht, bevorzugt eine mittels rotierendem Plasmabrenner thermisch gespritzte Schicht, und die thermisch gespritzte Schicht bildet zumindest teilweise die Manteloberfläche der Bohrung und kann dort als funktionale Schicht wirken. Die funktionale Schicht kann im Folgenden bevorzugt auch als eine Funktionsschicht verstanden werden, besonders bevorzugt auch als eine thermisch gespritzte Funktionsschicht.The layer system comprises at least one thermally sprayed layer, in particular a thermally sprayed layer by means of plasma spraying, preferably a layer thermally sprayed by means of a rotating plasma torch, and the thermally sprayed layer at least partially forms the jacket surface of the bore and can act there as a functional layer. In the following, the functional layer can preferably also be understood as a functional layer, particularly preferably also as a thermally sprayed functional layer.

Kern des Verfahrens ist das Aufbringen einer Haftschicht direkt auf das Grundmaterial des Zylinderbohrmantels, wobei die Haftschicht zumindest mit dem Grundmaterial eine chemische Verbindung eingeht. Die Haftschicht kann das Grenzflächenmaterial umfassen, insbesondere aus dem Grenzflächenmaterial bestehen. Die Haftschicht kann aus dem Grenzflächenmaterial aufgebaut sein. Hierdurch wird die Haftung an der Grenzfläche zum Grundmaterial also nicht ausschlaggebend durch mechanische Verzahnung sondern im Wesentlichen durch chemische Bindung erreicht.The core of the process is the application of an adhesive layer directly to the base material of the cylinder casing, the adhesive layer entering into a chemical bond at least with the base material. The adhesive layer can comprise the interface material, in particular consist of the interface material. The adhesive layer can be built up from the interface material. As a result, the adhesion to the interface with the base material is not primarily achieved through mechanical interlocking but essentially through chemical bonding.

Das Grenzflächenmaterial umfasst Molybdän (Mo) und mindestens ein weiteres Element, kann aber insbesondere auch im Wesentlichen aus Molybdän und mindestens einem weiteren Element bestehen, im Speziellen kann das Grenzflächenmaterial aus Molybdän und mindestens einem weiteren Element bestehen. Ist in der vorliegenden Beschreibung oder in den Ansprüchen vom Vorhandensein eines weiteren Elements die Rede, so kann dies, muss aber nicht in elementarer Form vorliegen sondern kann auch als Molekül und/oder innerhalb einer chemischen Verbindung vorhanden sein.The interface material comprises molybdenum (Mo) and at least one further element, but can in particular also essentially consist of molybdenum and at least one further element; in particular, the interface material can consist of molybdenum and at least one further element. If the presence of a further element is mentioned in the present description or in the claims, this can, but does not have to be, present in elemental form, but can also be present as a molecule and / or within a chemical compound.

In Ausgestaltung der Erfindung kann der Anteil an Molybdän am Grenzflächenmaterial, insbesondere an der Haftschicht, in einem Bereich von 30 bis 90 Gew.-% liegen und der Anteil des weiteren Elements am Grenzflächenmaterial, insbesondere an der Haftschicht, in einem Bereich von 70 bis 10 Gew.-% liegen, bevorzug der Anteil an Molybdän am Grenzflächenmaterial in einem Bereich von 40 bis 80 Gew.-% und der Anteil des weiteren Elements am Grenzflächenmaterial in einem Bereich von 60 bis 20 Gew.-% liegen, besonders bevorzugt der Anteil an Molybdän am Grenzflächenmaterial in einem Bereich von 50 bis 70 Gew.-% und der Anteil des weiteren Elements am Grenzflächenmaterial in einem Bereich von 50 bis 30 Gew.-% liegen. Im Speziellen kann der Anteil an Molybdän am Grenzflächenmaterial in einem Bereich von 55 bis 65 Gew.-% oder von 58 bis 62 Gew.-% oder bei 60 Gew.-%.und der Anteil des weiteren Elements am Grenzflächenmaterial in einem Bereich von 45 bis 35 Gew.-% oder von 42 bis 38 Gew.-% oder bei 40 Gew.-%.liegen. Das Grenzflächenmaterial kann ausserdem auch einen Anteil an Verunreinigungen, beispielsweise S und P im Bereich von 0.01 bis 0.2 Gew.-%, bevorzugt 0.01 bis 0.1 Gew.-% umfassen.In an embodiment of the invention, the proportion of molybdenum in the interface material, in particular in the adhesive layer, can be in a range from 30 to 90% by weight and the The proportion of the further element in the interface material, in particular in the adhesive layer, is in a range from 70 to 10% by weight, preferably the proportion of molybdenum in the interface material in a range from 40 to 80% by weight and the proportion of the further element in the Interface material lie in a range from 60 to 20% by weight, particularly preferably the proportion of molybdenum in the interface material in a range from 50 to 70% by weight and the proportion of the further element in the interface material in a range from 50 to 30% by weight. -% lie. In particular, the proportion of molybdenum in the interface material can be in a range from 55 to 65% by weight or from 58 to 62% by weight or at 60% by weight and the proportion of the further element in the interface material in a range from 45% to 35% by weight or from 42 to 38% by weight or at 40% by weight. The interface material can also contain a proportion of impurities, for example S and P, in the range from 0.01 to 0.2% by weight, preferably 0.01 to 0.1% by weight.

In Ausgestaltung der Erfindung kann das weitere Element und/oder die Funktionsschicht die folgenden Materialien umfassen, insbesondere aus den folgenden Materialien bestehen:
Für das weitere Element und/oder die Funktionsschicht kann ein Material, bevorzugt ein eisenbasiertes Material (im Folgenden auch Fe-Base genannt) in Form eines Pulvers, insbesondere ein gasverdüstes Pulver folgender chemischer Zusammensetzung eingesetzt werden:

  • C = 0,4 bis 1,5 Gewichts-%
  • Cr = 0,2 bis 2,5 Gewichts-%
  • Mn = 0,2 bis 3 Gewichts-%
  • Fe = Differenz auf 100 Gewichts-%,
insbesondere kann das Pulver zusätzlich enthalten:
  • S = 0,01 bis 0,2 Gewichts-%
  • P = 0,01 bis 0,1 Gewichts-%.
In an embodiment of the invention, the further element and / or the functional layer can comprise the following materials, in particular consist of the following materials:
For the further element and / or the functional layer, a material, preferably an iron-based material (hereinafter also referred to as Fe base) in the form of a powder, in particular a gas-atomized powder of the following chemical composition, can be used:
  • C = 0.4 to 1.5% by weight
  • Cr = 0.2 to 2.5% by weight
  • Mn = 0.2 to 3% by weight
  • Fe = difference to 100% by weight,
in particular, the powder can also contain:
  • S = 0.01 to 0.2% by weight
  • P = 0.01 to 0.1% by weight.

Bevorzugt kann für das weitere Element und/oder die Funktionsschicht das Fe-Base in Form eines Pulvers, insbesondere ein gasverdüstes Pulver folgender chemischer Zusammensetzung eingesetzt werden:

  • C = 0,1 bis 0,8 Gewichts-%
  • Cr = 11 bis 18 Gewichts-%
  • Mn = 0,1 bis 1,5 Gewichts-%
  • Mo = 0,1 bis 5 Gewichts-%
  • Fe = Differenz auf 100 Gewichts-%,
insbesondere kann das Pulver zusätzlich enthalten:
  • S = 0,01 bis 0,2 Gewichts-%
  • P = 0,01 bis 0,1 Gewichts-%.
The Fe base in the form of a powder, in particular a gas-atomized powder of the following chemical composition, can preferably be used for the further element and / or the functional layer:
  • C = 0.1 to 0.8% by weight
  • Cr = 11 to 18% by weight
  • Mn = 0.1 to 1.5% by weight
  • Mo = 0.1 to 5% by weight
  • Fe = difference to 100% by weight,
in particular, the powder can also contain:
  • S = 0.01 to 0.2% by weight
  • P = 0.01 to 0.1% by weight.

Das weitere Element und/oder die Funktionsschicht kann aber auch ein Fe-Base Material mit folgender chemischer Zusammensetzung sein Fe0.2C1.4Cr1.4Mn, insbesondere auch Mo = 0,1 bis 5 Gew.-% enthalten.The further element and / or the functional layer can, however, also contain an Fe base material with the following chemical composition: Fe0.2C1.4Cr1.4Mn, in particular also Mo = 0.1 to 5% by weight.

Die Partikelgrösse des Pulvers des weiteren Elements und/oder der Funktionsschicht kann im Bereich von 5 bis 25 µm oder 10 bis 45 µm oder 15 bis 60 µm liegen.The particle size of the powder of the further element and / or the functional layer can be in the range from 5 to 25 μm or 10 to 45 μm or 15 to 60 μm.

Das weitere Element und/oder die Funktionsschicht können aber auch die folgenden Materialien umfassen, insbesondere aus den folgenden Materialien bestehen:

  • Fe-Base + 30% Mo - im Speziellen Fe0.2C1.4Cr1.4Mn + 30% Mo
  • MMC=Metal Matrix Composite aus Fe-Base und einer Oxydkeramik, insbesondere einer tribologischen Oxydkeramik, bevorzugt eine Oxydkeramik die aus TiO2 oder aus Al2O3TiO2- und/oder Al2O3ZrO2- und/oder Al2O3-20ZrO2-Legierungssystemen besteht, und/oder der Anteil an Oxydkeramik im eingesetzten Material, insbesondere Pulver, 5 bis 50 Gew.-%, bevorzugt 35 Gew.-% beträgt. Im Speziellen kann das MMC hierbei Fe14Cr2Mo und 5 bis 50 Gew.-%, bevorzugt 35 Gew.-% der Oxydkeramik sein.
  • Vollkeramiken wie TiO2 oder Cr2O3
  • Cr3C2-25NiCr, insbesondere Cr3C2-25NiCr und 20% Mo
  • AISi und eine Keramik (wie Bsp. TiO2, ZnO2), insbesondere AISi und 20 Gew.-% Mo und eine Keramik.
The further element and / or the functional layer can, however, also comprise the following materials, in particular consist of the following materials:
  • Fe base + 30% Mo - especially Fe0.2C1.4Cr1.4Mn + 30% Mo
  • MMC = Metal Matrix Composite of Fe base and an oxide ceramic, in particular a tribological oxide ceramic, preferably an oxide ceramic made of TiO2 or of Al2O3TiO2 and / or Al2O3ZrO2 and / or Al2O3-20ZrO2 alloy systems, and / or the proportion of oxide ceramic in the material used, in particular powder, is 5 to 50% by weight, preferably 35% by weight. In particular, the MMC can be Fe14Cr2Mo and 5 to 50% by weight, preferably 35% by weight, of the oxide ceramic.
  • All ceramics such as TiO2 or Cr2O3
  • Cr3C2-25NiCr, especially Cr3C2-25NiCr and 20% Mo
  • AISi and a ceramic (such as TiO2, ZnO2), in particular AISi and 20% by weight of Mo and a ceramic.

Ist in der vorliegenden Beschreibung oder in den Ansprüchen von einer Haftschicht beispielsweise innerhalb eines Schichtsystems die Rede, so muss diese nicht unbedingt mit einer wohl definierten Grenzfläche zu der oder den anderen Schichten des Schichtsystems ausgebildet sein, sofern nichts anderes definiert ist. Beispielsweise kann diese über einen Zusammensetzungsgradienten in eine andere Schicht übergehen, oder es kann aufgrund von Grenzflächenprofilierung an einer wohldefinierten Schicht fehlen.If an adhesive layer is mentioned in the present description or in the claims, for example within a layer system, it does not necessarily have to be formed with a well-defined interface to the other layer or layers of the layer system, unless otherwise defined. For example, this can merge into another layer via a composition gradient, or a well-defined layer can be missing due to interface profiling.

Ist in der vorliegenden Beschreibung oder in den Ansprüchen vom Vorhandensein eines chemischen Elementes die Rede, so muss dies nicht in elementarer Form vorliegen sondern kann auch innerhalb einer chemischen Verbindung vorhanden sein.If the presence of a chemical element is mentioned in the present description or in the claims, this does not have to be present in elemental form but can also be present within a chemical compound.

Gemäss einer bevorzugten ersten Ausgestaltungsform der vorliegenden Erfindung ist das Material der Haftschicht ausserdem so gewählt, dass dieses Material auch mit dem Material der aufzubringenden thermisch gespritzten Funktionsschicht eine chemische Verbindung eingeht und damit haftet.According to a preferred first embodiment of the present invention, the material of the adhesive layer is also selected such that this material also forms a chemical bond with the material of the thermally sprayed functional layer to be applied and thus adheres.

Erfindungsgemäß wird die Haftschicht so ausgestaltet, dass sie eine Porosität und/oder Kolumnarität aufweist, welche dazu führt dass die aufzubringende thermisch gespritzte Funktionsschicht zumindest mechanisch auf der Haftschicht in ausreichendem Masse haftet. Beispielsweise kann dies durch gezielt kolumnares Wachstum erreicht werden. Es ist auch möglich dies mittels erhöhter Porosität zu erreichen.According to the invention, the adhesive layer is designed in such a way that it has a porosity and / or columnarity which leads to the thermally sprayed functional layer to be applied adhering sufficiently at least mechanically to the adhesive layer. For example, this can be achieved through targeted columnar growth. It is also possible to achieve this by means of increased porosity.

Figur 2 zeigt eine erfindungsgemässe Ausführungsform, gemäss der die Haftung der gespritzten Funktionsschicht 3 auf dem Grundmaterial 1 ohne Aktivierung der Oberfläche des Grundmaterials 1 durch chemische Bindung zwischen der Haftschicht 5 und dem Grundmaterial 1 und durch mechanische und/oder chemische Bindung zwischen Haftschicht 5 und Funktionsschicht 3 gewährleistet ist. Figure 2 shows an embodiment according to the invention, according to which the adhesion of the sprayed functional layer 3 to the base material 1 is ensured without activating the surface of the base material 1 by chemical bonding between the adhesive layer 5 and the base material 1 and by mechanical and / or chemical bonding between the adhesive layer 5 and the functional layer 3 is.

In Ausgestaltung kann die Beschichtung der Zylinderbohrung, insbesondere das Schichtsystem in Form eines graduellen Übergangs und/oder eines Gradienten ausgestaltet sein, insbesondere in der chemischen Zusammensetzung und/oder dem strukturellen Aufbau. Auf diese Weise liegt also eigentlich nur eine Schicht vor mit graduell sich ändernder Zusammensetzung und/oder Morphologie, also eine graduelle Schicht, insbesondere ein graduelles Schichtsystem. Unter einer graduellen Schicht, insbesondere einem graduellen Schichtsystem, kann also verstanden werden, dass die graduelle Schicht direkt an der ersten Grenzfläche dann Material umfasst, welche mit der Oberfläche des Grundmaterials des Zylinders eine chemische Bindung eingehen, also insbesondere das Material der Haftschicht, also das Grenzflächenmaterial. Mit zunehmendem Abstand von dieser Oberfläche, d.h. mit zunehmender Schichtdicke geht das Schichtmaterial dann graduell in das Schichtmaterial der eigentlich aufzubringenden schützenden thermisch gespritzte Schicht, bevorzugt die Funktionsschicht, über.In one embodiment, the coating of the cylinder bore, in particular the layer system, can be designed in the form of a gradual transition and / or a gradient, in particular in terms of the chemical composition and / or the structural structure. In this way, there is actually only one layer with a gradually changing composition and / or morphology, that is to say a gradual layer, in particular a gradual layer system. A gradual layer, in particular a gradual layer system, can therefore be understood to mean that the gradual layer then directly at the first interface comprises material which forms a chemical bond with the surface of the base material of the cylinder, i.e. in particular the material of the adhesive layer, i.e. the Interface material. With increasing distance from this surface, i.e. with increasing layer thickness, the layer material then gradually changes into the layer material of the protective thermally sprayed layer that is actually to be applied, preferably the functional layer.

In Ausgestaltung der Erfindung kann die graduelle Schicht, insbesondere das graduelle Schichtsystem, mit der graduell sich ändernden Zusammensetzung, also dem graduellen Übergang und/oder dem Gradienten, die folgenden beiden Varianten umfassen:In an embodiment of the invention, the gradual layer, in particular the gradual layer system, with the gradually changing composition, that is to say the gradual transition and / or the gradient, can comprise the following two variants:

Variante 1version 1

Das Grenzflächenmaterial geht graduell in das Material der funktionalen Schicht, insbesondere in die Funktionsschicht, über, wobei gilt:
Start der Schicht mit der graduell sich ändernden Zusammensetzung an der ersten Grenzfläche mit 0 Gew.-% Material der Funktionsschicht und 100 Gew.-% Grenzflächenmaterial, wobei das Grenzflächenmaterial 60 Gew.-% Molybdän und 40 Gew.-% weiteres Element umfassen kann, bevorzugt das Grenzflächenmaterial aus 60% Gew.-% Molybdän und 40 Gew.-% Ni5Al bestehen kann. Ende der Schicht mit der graduell sich ändernden Zusammensetzung mit 100 Gew.-% Anteil Funktionsschicht und 0 Gew.-% Anteil Grenzflächenmaterial, sodass das Ende der graduellen Schicht, zumindest teilweise die Manteloberfläche der Bohrung des Zylinders bildet und dort als Funktionsschicht wirken kann.The interface material gradually changes into the material of the functional layer, in particular into the functional layer, where:
Start of the layer with the gradually changing composition at the first interface with 0% by weight of material of the functional layer and 100% by weight of interface material, whereby the interface material can comprise 60% by weight of molybdenum and 40% by weight of further element, preferably the interface material can consist of 60% by weight molybdenum and 40% by weight Ni5Al. End of the layer with the gradually changing composition with 100% by weight of functional layer and 0% by weight of interface material, so that the end of the gradual layer at least partially forms the outer surface of the bore of the cylinder and can act there as a functional layer.

Variante 2Variant 2

Das Grenzflächenmaterial kann Molybdän und das weitere Element umfassen, insbesondere aus diesem bestehen, wobei das weitere Element bevorzugt dem Material der Funktionsschicht entsprechen kann, und das Grenzflächenmaterial geht graduell in das Material der Funktionsschicht über, insbesondere die Haftschicht in die Funktionsschicht über, wobei gilt:
Start der Schicht mit der graduell sich ändernden Zusammensetzung an der ersten Grenzfläche mit 40 Gew.-% Anteil weiteres Element und 50 bis 70 Gew.-%, bevorzugt 60 Gew.-% Molybdän. Ende der Schicht mit der graduell sich ändernden Zusammensetzung mit 0 bis 40 Gew.-% Anteil Molybdän und 60 bis 100 Gew.-% Anteil weiterem Element, das insbesondere dem Material der Funktionsschicht entspricht, bevorzugt 20 bis 40 Gew.-% Anteil Molybdän und 60 bis 80 Gew.-% Anteil weiterem Element, besonders bevorzugt 30 Gew.-% Anteil Molybdän und 70 Gew.-% Anteil weiterem Element, sodass das Ende der graduellen Schicht, zumindest teilweise die innere Manteloberfläche der Bohrung des Zylinders bildet und dort als Funktionsschicht wirken kann.The interface material can comprise molybdenum and the further element, in particular consist of this, wherein the further element can preferably correspond to the material of the functional layer, and the interface material gradually merges into the material of the functional layer, in particular the adhesive layer merges into the functional layer, where:
Start of the layer with the gradually changing composition at the first interface with 40% by weight of additional element and 50 to 70% by weight, preferably 60% by weight of molybdenum. End of the layer with the gradually changing composition with 0 to 40% by weight of molybdenum and 60 to 100% by weight of further element, which in particular corresponds to the material of the functional layer, preferably 20 to 40% by weight of molybdenum and 60 to 80% by weight proportion of further element, particularly preferably 30% by weight proportion of molybdenum and 70% by weight proportion of further element, so that the end of the gradual layer, at least partially forms the inner jacket surface of the bore of the cylinder and can act there as a functional layer.

Beispielsweise kann Variante 2 dann die folgenden chemische Zusammensetzung und den folgenden Verlauf aufweisen:For example, variant 2 can then have the following chemical composition and the following course:

Beispiel 1:Example 1:

Weiteres Element=Fe-Base, insbesondere Funktionsschicht=weiteres Element=Fe-Base

  • Start: Fe-Base und 60 Gew.-% Molybdän, bevorzugt Fe0.2C1.4Cr1.4Mn + 60% Mo
  • Ende: Fe-Base, bevorzugt Fe0.2C1.4Cr1.4Mn
Another element = Fe base, in particular functional layer = another element = Fe base
  • Start: Fe base and 60% by weight molybdenum, preferably Fe0.2C1.4Cr1.4Mn + 60% Mo
  • End: Fe base, preferably Fe0.2C1.4Cr1.4Mn

Beispiel 2:Example 2:

Weiteres Element=Fe-Base, insbesondere Funktionsschicht=weiteres Element=Fe-Base

  • Start: Fe-Base und 60 Gew.-% Molybdän, bevorzugt Fe0.2C1.4Cr1.4Mn + 60% Molybdän
  • Ende: Fe-Base und 30 Gew.-% Molybdän, bevorzugt Fe0.2C1.4Cr1.4Mn + 30% Molybdän
Another element = Fe base, in particular functional layer = another element = Fe base
  • Start: Fe base and 60% by weight molybdenum, preferably Fe0.2C1.4Cr1.4Mn + 60% molybdenum
  • End: Fe base and 30% by weight molybdenum, preferably Fe0.2C1.4Cr1.4Mn + 30% molybdenum

In Ausgestaltung der Erfindung kann der Anteil des Grenzflächenmaterials an der graduellen Schicht mit der graduell sich ändernden Zusammensetzung vom Start zum Ende bevorzugt linear oder exponentiell abnehmen, insbesondere bei der Variante 1 und/oder der Variante 2, und/oder der Anteil der Funktionsschicht an der Schicht mit der graduell sich ändernden Zusammensetzung kann bevorzugt vom Start zum Ende linear oder exponentiell zunehmen, insbesondere bei der Variante 1 und/oder der Variante 2.In an embodiment of the invention, the proportion of the interface material in the gradual layer with the gradually changing composition from the start to the end can preferably decrease linearly or exponentially, in particular in variant 1 and / or variant 2, and / or the proportion of the functional layer in the The layer with the gradually changing composition can preferably increase linearly or exponentially from start to finish, in particular in the case of variant 1 and / or variant 2.

Gemäss einer besonders bevorzugten dritten Ausführungsform der vorliegenden Erfindung wird die Beschichtung der Zylinderbohrung in Form eines Gradienten ausgestaltet. Direkt an der Grenzfläche umfasst die aufzubringende Schicht dann Materialien, welche mit der Oberfläche des Grundmaterials des Zylinders eine chemische Bindung eingehen, also insbesondere das Material der Haftschicht. Mit zunehmendem Abstand von dieser Oberfläche, d.h. mit zunehmender Schichtdicke geht das Schichtmaterial dann graduell in das Schichtmaterial der eigentlich aufzubringenden schützenden thermisch gespritzte Schicht über. Die könnte beispielsweise über eine Doppelinjektion mit zeitlich abnehmender Injektion der Haftschicht und/oder zeitlich zunehmender Injektion der Funktionsschicht, realisiert werden. Auf diese Weise liegt also eigentlich nur eine Schicht vor mit graduell sich ändernder Zusammensetzung und/oder Morphologie, also eine graduelle Schicht, insbesondere ein graduelles Schichtsystem.According to a particularly preferred third embodiment of the present invention, the coating of the cylinder bore is designed in the form of a gradient. Directly at the interface, the layer to be applied then comprises materials which enter into a chemical bond with the surface of the base material of the cylinder, that is to say in particular the material of the adhesive layer. With increasing distance from this surface, i.e. with increasing layer thickness, the layer material then gradually merges into the layer material of the protective thermally sprayed layer that is actually to be applied. This could be implemented, for example, via a double injection with the injection of the adhesive layer decreasing over time and / or the injection of the functional layer increasing over time. In this way, there is actually only one layer with a gradually changing composition and / or morphology, that is to say a gradual layer, in particular a gradual layer system.

In Ausgestaltung der Erfindung kann die Schicht mit der graduell sich ändernden Zusammensetzung, also dem graduellen Übergang, d.h. eine gradierende Schicht, auch durch eine Einzelinjektion realisiert werden, wobei zwei getrennte Zuführungen für das Material der Haftschicht und die Funktionsschicht verwendet werden können, insbesondere zwei Pulverförderer, die in einem Y-förmigen Bauteil zusammengeführt werden.In an embodiment of the invention, the layer with the gradually changing composition, ie the gradual transition, ie a grading layer, can also be implemented by a single injection, with two separate feeds for the The material of the adhesive layer and the functional layer can be used, in particular two powder feeders which are brought together in a Y-shaped component.

Als Beispiel für eine solche Haftschicht lässt sich eine Materialzusammensetzung angeben welche NiAl und Mo umfasst.As an example of such an adhesive layer, a material composition can be specified which comprises NiAl and Mo.

In Ausgestaltung der Erfindung kann das Grenzflächenmaterial Molybdän und Ni5Al umfassen, bevorzugt aus Molybdän und Ni5AI bestehen. Die folgende Tabelle 1 zeigt die durchschnittlich erreichten Haftzugfestigkeiten bei herkömmlicher bekannter Aktivierung (mechanisch, Korund) und bei einem Grenzflächenmaterial bestehend aus Molybdän und Ni5Al, insbesondere kann das Grenzflächenmaterial auch aus Molybdän und Ni5Al und einem Anteil an Verunreinigungen im Bereich von 0.1 bis 0.3 Gew.-% bestehen. Tabelle 1: Vergleich der Haftzugfestigkeiten bei herkömmlicher bekannter Aktivierung und bei einem Grenzflächenmaterial bestehend aus Molybdän und Ni5Al. Anteil Molybdän an Haftschicht [Gew.-%] Anteil Ni5AI an Haftschicht [Gew.-%] Art der Aktivierung/ Haftschicht Durchschnittliche Haftzugfestigkeit [Mpa] None None Mit Korund aktiviert 18.1 None None Mechanisch aktiviert 35.2 30 70 Haftschicht 40.8 40 60 Haftschicht 41.5 60 40 Haftschicht 44.0 70 30 Haftschicht 41.0 90 10 Haftschicht 30.0 In an embodiment of the invention, the interface material can comprise molybdenum and Ni5Al, preferably consist of molybdenum and Ni5Al. The following table 1 shows the average tensile strengths achieved with conventional, known activation (mechanical, corundum) and with an interface material consisting of molybdenum and Ni5Al, in particular the interface material can also consist of molybdenum and Ni5Al and a proportion of impurities in the range from 0.1 to 0.3 wt. -% exist. Table 1: Comparison of the adhesive tensile strengths with conventionally known activation and with an interface material consisting of molybdenum and Ni5Al. Proportion of molybdenum in the adhesive layer [% by weight] Proportion of Ni5AI in the adhesive layer [% by weight] Type of activation / adhesive layer Average adhesive tensile strength [Mpa] None None Activated with corundum 18.1 None None Mechanically activated 35.2 30th 70 Adhesive layer 40.8 40 60 Adhesive layer 41.5 60 40 Adhesive layer 44.0 70 30th Adhesive layer 41.0 90 10 Adhesive layer 30.0

Die Erfindung wird nun mit anhand eines Beispiels und mit Hilfe der Figuren im Detail dargestellt.

Figur 1
zeigt den bisherigen Stand der Technik
Figur 2
zeigt ein erstes Ausführungsbeispiel der vorliegenden Erfindung
Figur 3
zeigt ein zweites Ausführungsbeispiel der vorliegenden Erfindung.
The invention will now be illustrated in detail with the aid of an example and with the aid of the figures.
Figure 1
shows the current state of the art
Figure 2
Fig. 3 shows a first embodiment of the present invention
Figure 3
Fig. 3 shows a second embodiment of the present invention.

Das Beispiel bezieht sich auf die Erfindung gemäss der ersten Ausführungsform. Es wird die Bohrung eines Zylinders beschichtet, wobei das Grundmaterial des Zylinders eine Aluminium-Legierung ist und die Bohrung einen Durchmesser von 85 mm aufweist und die Bohrung 170 mm tief ist. Diese Bohrung soll mit einer thermisch gespritzten Schicht auf Eisenbasis (95% Fe, 1.5% Cr, 1%Mn, 1% C) beschichtet werden, die eine Dicke von 200 - 300 Mikrometer aufweist. Als Beschichtungmethode des thermischen Spritzens soll atmosphärisches Plasma-Spritzen (APS) verwendet werden. Hierbei wird unter Zuführung von Energie und Prozessgasen pulverförmiges Beschichtungsmaterial in einem Plasma kontinuierlich zum Schmelzen gebracht , flüssig zerstäubt und dann auf das Grundmaterial der Zylinderwandung innen aufgebracht wo es erstarrt und eine geschlossene Schicht bildet. Der Plasmabrenner rotiert dabei während des Schmelzvorgangs so dass die Zylinderwandung innen rundherum gleichmässig mit Schicht beauftragt wird.The example relates to the invention according to the first embodiment. The bore of a cylinder is coated, the base material of the cylinder being an aluminum alloy and the bore having a diameter of 85 mm and the bore 170 mm deep. This hole is to be coated with a thermally sprayed iron-based layer (95% Fe, 1.5% Cr, 1% Mn, 1% C) that is 200-300 micrometers thick. Atmospheric plasma spraying (APS) should be used as the coating method for thermal spraying. With the supply of energy and process gases, powdery coating material is continuously melted in a plasma, atomized in liquid form and then applied to the inside of the base material of the cylinder wall, where it solidifies and forms a closed layer. The plasma torch rotates during the melting process so that the inside of the cylinder wall is evenly coated with a layer.

Würde diese Schicht mittels der beschriebenen Methode einfach direkt auf das Grundmaterial aufgebracht, so würde diese nicht ausreichend auf dem Grundmaterial haften. Gemäss Stand der Technik könnte die Oberfläche des Grundmaterials nun aufgeraut werden oder profiliert werden.If this layer were simply applied directly to the base material using the method described, it would not adhere sufficiently to the base material. According to the state of the art, the surface of the base material could now be roughened or profiled.

Demgegenüber wird erfindungsgemäss im vorliegenden Beispiel direkt auf das Grundmaterial eine 5 - 150 Mikrometer dicke Haftschicht aus einer Mischung von Molybdän und Nickel-Aluminium Pulver aufgebracht. Dieses Material hat den Vorteil, dass es sowohl mit dem Grundmaterial als auch mit dem eigentlichen Schichtmaterial chemische Bindungen eingeht. An der Grenzfläche zum Grundmaterial entstehen also chemische Verbindungen beispielsweise ionischer Natur und an der Grenzfläche der Haftschicht zum Schichtmaterial entstehen ebenfalls ionische Bindungen und zusätzlich mechanisch Verhakung durch die raue Spritzschicht. Hierdurch ist an beiden Grenzflächen eine ausreichende Haftung gewährleistet.In contrast, in the present example according to the invention, a 5-150 micrometer thick adhesive layer made of a mixture of molybdenum and nickel-aluminum powder is applied directly to the base material. This material has the advantage that it forms chemical bonds both with the base material and with the actual layer material. Chemical compounds of an ionic nature, for example, arise at the interface with the base material, and ionic bonds and, in addition, mechanical entanglement due to the rough spray coating, also arise at the interface between the adhesive layer and the layer material. This ensures adequate adhesion at both interfaces.

Claims (13)

  1. A cylinder of a piston-type internal combustion engine, wherein the cylinder comprises at least one bore with an inner shell formed from a base material, wherein in the region of the bore the base material is at least partially provided with a layer system and a first boundary surface is thus formed between the base material and the layer system and the layer system comprises at least one thermally sprayed layer and the thermally sprayed layer forms at least partially the shell surface of the bore and can act there as a functional layer and wherein the first boundary surface does not comprise any profiling applied for the activation of the surface apart from the surface roughness resulting from the manufacture of the bore, wherein the material of the layer system comprises molybdenum and at least one further element in the region of the first boundary surface to the base material, hereinafter referred to as the boundary surface material, and is bonded to the base material by a chemical bond and the boundary surface material differs from the material of the functional layer in its composition and / or structure, characterized in that the region comprising the boundary surface material between base material and functional layer is produced as a base layer forming a second boundary surface to the functional layer in such a way that the second boundary surface has structures suitable for mechanical activation in the form of porosity and / or columnarity.
  2. A cylinder according to claim 1, characterized in that structural means for the cohesion of the layer system are provided within the layer system.
  3. A cylinder according to claim 2, characterized in that the structural means comprise chemical bonds and / or boundary surfaces roughnesses, which have preferably been created by the application process of the boundary surface material and / or by a gradual transition from boundary surface material to the material of the functional layer.
  4. A cylinder according to anyone of the claims 1 to 3, characterized in that the chemical bond between the boundary surface material to the base material is realized by ionic bonds and / or by covalent bonds.
  5. A cylinder according to anyone of the claims 1 to 4, characterized in that at least one chemical element which corresponds to a chemical element in the base material is present in the boundary surface material.
  6. A cylinder according to anyone of the preceding claims, characterized in that the layer system forms at least partially at least one gradient in the chemical composition and / or structural construction over the layer thickness, starting from the first boundary surface and continuing through the functional layer on the shell surface.
  7. A cylinder according to anyone of the preceding claims, characterized in that at least one chemical element, which corresponds to a chemical element in the functional layer, is present in the boundary surface material.
  8. A method of manufacturing a cylinder for a piston-type internal combustion engine having a bore, the method comprising the steps of:
    - providing a cylinder with a bore, wherein the inner shell of the bore is formed from a base material and the surface of which, apart from the surface roughness resulting from the manufacture of the bore, does not comprise any profiling for activating the surface.
    - applying the inner shell of the bore with a layer system, which comprises a boundary surface material at the boundary surface to the base material and wherein at least the layer of the layer system forming the surface of the cylinder bore is thermally sprayed and forms a functional layer,
    wherin the boundary surface material comprises molybdenum and at least one further element and is selected such that it forms a chemical bond with the base material and the layer system is applied in such a way that the boundary surface material and the material of the functional layer differ chemically in the composition and / or the structure characterized in that the region comprising the boundary surface material between base material and functional layer is produced as a base layer forming a second boundary surface to the functional layer in such a way that the second boundary surface has structures suitable for mechanical activation in the form of porosity and / or columnarity.
  9. A method according to anyone of the claims 8, characterized in that the layer system is applied completely by means of thermal spraying.
  10. A method according to anyone of the claims 8 and 9, characterized in that the layer system is formed at least partially as a gradient layer in the direction of the layer thickness.
  11. A method according to claim 10, characterized in that the layer system of the transition from the boundary surface material to the material of the functional layer is formed as a gradient.
  12. An engine having a cylinder according to anyone of the claims 1 to 7.
  13. A method of manufacturing an engine, characterized in that the method comprises the process steps according to anyone of the claims 8 to 11.
EP17739279.2A 2016-07-13 2017-07-13 Coating of cylindrical boreholes without previous activation of the coating Active EP3485056B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16179340 2016-07-13
PCT/EP2017/067748 WO2018011362A1 (en) 2016-07-13 2017-07-13 Coating cylinder bores without prior activation of the surface

Publications (2)

Publication Number Publication Date
EP3485056A1 EP3485056A1 (en) 2019-05-22
EP3485056B1 true EP3485056B1 (en) 2021-10-20

Family

ID=56740805

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17739279.2A Active EP3485056B1 (en) 2016-07-13 2017-07-13 Coating of cylindrical boreholes without previous activation of the coating

Country Status (6)

Country Link
US (1) US10920308B2 (en)
EP (1) EP3485056B1 (en)
JP (2) JP7166243B2 (en)
CN (1) CN109642306A (en)
CA (1) CA3030055C (en)
WO (1) WO2018011362A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10907569B2 (en) * 2019-06-19 2021-02-02 Ford Global Technologies, Llc Systems and methods for a cylinder bore coating fill material
CN113549857A (en) * 2021-07-21 2021-10-26 昆明理工大学 Self-lubricating coating for inner wall of engine cylinder hole and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2588422A (en) 1947-12-19 1952-03-11 Metallizing Engineering Co Inc Application of spray metal linings for aluminum engine cylinders of or for reciprocating engines
JPS5212846B2 (en) * 1973-05-04 1977-04-09
US4044217A (en) * 1975-05-07 1977-08-23 Kawasaki Jukogyo Kabushiki Kaisha Sliding surface working method using wire-explosion coating
JPS51141736A (en) * 1975-05-31 1976-12-06 Kawasaki Heavy Ind Ltd Production method for cylinder
DE3421569C1 (en) * 1984-06-09 1985-06-27 Goetze Ag, 5093 Burscheid Wear-resistant coating
JP2604423B2 (en) * 1988-05-30 1997-04-30 新日本製鐵株式会社 Super heat resistant inclined coating forming method
JP2559283B2 (en) * 1990-03-08 1996-12-04 帝国ピストンリング株式会社 piston ring
JPH04214850A (en) * 1990-12-14 1992-08-05 Fujitsu Ltd Film structure and its manufacture
JPH05195190A (en) * 1992-01-23 1993-08-03 Toyota Motor Corp Hard coating film formation on ti base material
JPH0711433A (en) * 1993-06-29 1995-01-13 Asahi Glass Co Ltd Target for sputtering and its production
JPH08246944A (en) * 1995-03-08 1996-09-24 Suzuki Motor Corp Cylinder for internal combustion engine and manufacture thereof
US20040105939A1 (en) * 2000-07-26 2004-06-03 Daimlerchrysler Ag Surface layer and process for producing a surface layer
US20050016489A1 (en) 2003-07-23 2005-01-27 Endicott Mark Thomas Method of producing coated engine components
US20050025896A1 (en) * 2003-08-01 2005-02-03 Grigoriy Grinberg Thermal spray metal on low heat resistant substrates
JP2005307857A (en) 2004-04-21 2005-11-04 Toyota Motor Corp Cylinder block and its manufacturing method
JP4491385B2 (en) * 2005-07-08 2010-06-30 トヨタ自動車株式会社 Casting parts, cylinder block and cylinder liner manufacturing method
US8505438B2 (en) * 2008-12-29 2013-08-13 Yoosung Enterprise Co., Ltd. Cylinder liner and method of manufacturing the same
US20140199163A1 (en) * 2011-03-09 2014-07-17 Rolls-Royce Corporation- Abradable layer including a low thermal conductivity composition
DE102012216518A1 (en) * 2012-09-17 2014-03-20 Federal-Mogul Burscheid Gmbh Cylinder liner with wear-resistant inner layer
EP3071733A1 (en) * 2013-11-18 2016-09-28 Ford Otomotiv Sanayi Anonim Sirketi Layered thermal barrier coating and coating method
DE102014011139A1 (en) * 2014-07-25 2015-01-08 Daimler Ag engine component
DE102015213896A1 (en) 2015-07-23 2017-01-26 Volkswagen Aktiengesellschaft Process for coating a metallic tool and component

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
CA3030055C (en) 2024-03-19
WO2018011362A1 (en) 2018-01-18
JP2022191217A (en) 2022-12-27
CA3030055A1 (en) 2018-01-18
JP7166243B2 (en) 2022-11-07
EP3485056A1 (en) 2019-05-22
US20190292644A1 (en) 2019-09-26
US10920308B2 (en) 2021-02-16
CN109642306A (en) 2019-04-16
JP2019524997A (en) 2019-09-05

Similar Documents

Publication Publication Date Title
EP2464761B1 (en) Piston ring with a coating.
EP1980773B1 (en) Thermal spraying method for coating a piston ring groove, application of a spray wire and piston with a thermal spray coating
EP3325685B1 (en) Method for coating a cylinder barrel of a cylinder crankcase, cylinder crankcase with a coated cylinder barrel and engine
DE102011086803A1 (en) Repair method of a cylinder surface by means of plasma spraying
EP3485056B1 (en) Coating of cylindrical boreholes without previous activation of the coating
EP2113036B1 (en) Method for the production of a fiber composite comprising a metallic matrix
EP0770698B2 (en) Process for manufacture of a sliding surface on a metallic workpiece
DE102013223011A1 (en) Process for producing a coated surface of a tribological system
EP2829713B1 (en) Workpiece with a recess for holding a piston
EP3601629B1 (en) Piston ring with shot-peened running-in layer and method for the production thereof
DE102006057839A1 (en) Cylinder for a combustion engine comprises a tapered section formed as a material coating applied on the running surface of the cylinder in the region above an upper annular mirror point
DE08763070T1 (en) METHOD AND DEVICE FOR PRODUCING A DEEP-DRILL MOTOR RADIAL BEARING
DE102009025621A1 (en) Method for manufacturing of metallic component with hardened upper surface layer, involves hardening upper surface layer by knocking or hammering operation by impact head
DE102012018706B3 (en) Method for manufacturing piston ring of internal combustion engine, involves producing piston ring main body with groove in running surface, providing carrier body with hard material coating and inserting coated carrier body into groove
DE102012005174A1 (en) Piston ring e.g. pressure ring, for use in groove of piston of e.g. diesel engine, has bonding layer made of pure chromium material and arranged between lower and exterior layers of outer peripheral front side of main annular metallic base
DE102014011139A1 (en) engine component
EP2616567B1 (en) Method of thermal coating
DE102013221375A1 (en) Method for producing a coated bore surface, in particular a cylinder bore
DE102015216969A1 (en) Coated sintered material, process for its production and uses of the coated sintered material
DE102012201342A1 (en) Method for producing inner surface of cylinder bore with local different roughness structures of reciprocating piston-internal combustion engine, involves fine drilling or pre-honing hole inner surface, and completely honing inner surface
WO2016139007A1 (en) Method for producing a bearing surface for a seal
DE102014202135B4 (en) Method for coating a bore, cylinder lining and cylinder block of an internal combustion engine
DE102016216882A1 (en) Method for producing a hydraulic component and hydraulic component
DE102011013207B4 (en) Component blank and method, forming tool and forming device for producing a component with a hardened surface
DE102014221363A1 (en) Method for producing a coated cylinder bore of an internal combustion engine

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200218

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210527

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502017011781

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1440029

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211115

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20211020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220220

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220221

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220120

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220121

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502017011781

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220713

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220713

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230721

Year of fee payment: 7

Ref country code: AT

Payment date: 20230718

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20170713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211020

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240730

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240724

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240725

Year of fee payment: 8