EP3485056A1 - Coating cylinder bores without prior activation of the surface - Google Patents

Coating cylinder bores without prior activation of the surface

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Publication number
EP3485056A1
EP3485056A1 EP17739279.2A EP17739279A EP3485056A1 EP 3485056 A1 EP3485056 A1 EP 3485056A1 EP 17739279 A EP17739279 A EP 17739279A EP 3485056 A1 EP3485056 A1 EP 3485056A1
Authority
EP
European Patent Office
Prior art keywords
layer
interface
base material
bore
cylinder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17739279.2A
Other languages
German (de)
French (fr)
Other versions
EP3485056B1 (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
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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

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/18—Other cylinders
    • 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
    • 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
    • C23C4/12—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

Definitions

  • the cylinder bores of some piston internal combustion engines are usually provided with a coating by means of thermal spraying in order to minimize the weight and / or the friction and / or the wear. As a result, the fuel and oil consumption is reduced and preferably made the surface of the cylinder bore corrosion resistant.
  • the adhesion of this layer to the cylinder material is problematic, so that the layer is in danger of bursting during operation.
  • the surface of the cylinder bore is usually roughened (activated). Such activation ensures that a mechanical entanglement between layer and base material of the cylinder block is produced, i. it comes to a positive conclusion.
  • This pre-machining step of activating the cylinder tread increases the cost of the coating.
  • the entanglement between layer and base material of the cylinder block achieved by the activation improves the adhesion of the layer to the base material and contributes to a long service life of the cylinder.
  • Different techniques can be used to perform the activation.
  • the surface can be roughened by means of corundum jets, 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 of activation is to provide the surface with a profiling with undercuts, for example by means of machining. For example, here the dovetail geometry is used with advantage.
  • Figure 1 shows the mechanical entanglement of the sprayed layer 3 with the base material 1 by activation of the base material before coating.
  • the cylinder comprises at least one bore with an inner jacket which is formed from a base material, wherein in the region of the bore the base material is at least partially provided with a layer system.
  • a first boundary surface is formed between the base material and the layer system, wherein the first boundary surface, apart from the surface roughness created by the production of the bore, does not include any profiling applied for activating the surface, in particular does not include any profiling applied for the mechanical activation of the surface.
  • the layer system comprises at least one thermally sprayed layer, in particular a layer sprayed 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 method is the application of an adhesive layer directly to the base material of the cylinder bore casing, wherein the adhesive layer forms a chemical compound at least with the base material.
  • the adhesive layer may comprise the interface material, in particular consist of the interface material.
  • the adhesive layer may be composed of the interface material.
  • the interface material comprises molybdenum (Mo) and at least one further element, but may in particular also consist essentially of molybdenum and at least one further element, in particular the interface material may consist of molybdenum and at least one further element. If in the present description or in the claims the presence of a further element is mentioned, this may or may not be present in elemental form but may also be present as a molecule and / or within a chemical compound.
  • the proportion of molybdenum on the interface material, in particular on the adhesive layer, in a range of 30 to 90 wt .-% are and the Proportion of the further element on the interface material, in particular on the adhesive layer, in a range of 70 to 10 wt .-%,
  • the content of molybdenum in the interface material may be in a range of 55 to 65% by weight or 58 to 62% by weight or 60% by weight, and the proportion of the other element in the interface material may be in the range of 45 to 35% by weight or from 42 to 38% by weight or at 40% by weight. lie.
  • the interfacial material may also comprise a proportion of impurities, for example S and P in the range of 0.01 to 0.2 wt .-%, preferably 0.01 to 0.1 wt .-%.
  • the further element and / or the functional layer may comprise the following materials, in particular consisting of the following materials:
  • a material preferably an iron-based material (also referred to below as Fe base) in the form of a powder, in particular a gas atomized powder of the following chemical composition can be used:
  • the powder may additionally contain:
  • the Fe base in the form of a powder, in particular a gas-atomized powder of the following chemical
  • composition to be used is a composition to be used:
  • the powder may additionally contain:
  • the particle size of the powder of the further element and / or the functional layer may be in the range from 5 to 25 ⁇ m or 10 to 45 ⁇ m or 15 to 60 ⁇ m.
  • the further element and / or the functional layer may also comprise the following materials, in particular consisting of the following materials:
  • MMC metal matrix composite of Fe base and an oxide ceramic, in particular a tribological oxide ceramic, preferably an oxide ceramic consisting of TiO 2 or of ⁇ 203 ⁇ 02 and / or Al 2 O 3 ZrO 2 and / or Al 2 O 3 20ZrO 2 alloy systems, and / or the proportion of Oxydkeramik in the material used, in particular powder, 5 to 50 wt .-%, preferably 35 wt .-% is.
  • the MMC may be Fel4Cr2Mo and 5 to 50 wt%, preferably 35 wt%, of the oxide ceramic.
  • AISi and a ceramic such as Ti02, Zn02, in particular AISi and 20 wt .-% Mo and a ceramic.
  • an adhesive layer for example within a layer system is mentioned, it does not necessarily have to be formed with a well-defined interface to the one or more other layers of the layer system, unless otherwise defined. For example, it may transition to another layer via a composition gradient, or may lack a well-defined layer due to interfacial profiling.
  • the material of the adhesive layer is also chosen so that this material also enters into a chemical compound with the material of the thermally sprayed functional layer to be applied and thus adheres.
  • the adhesive layer is designed such that it has a surface roughness which results in the thermally sprayed functional layer to be applied adhering at least mechanically to the adhesive layer to a sufficient extent.
  • a corresponding roughness can be achieved by targeted columnar growth. It is also possible to achieve the roughness of the adhesive layer by means of increased porosity.
  • FIG. 2 shows an embodiment according to the invention according to which the adhesion of the sprayed functional layer 3 to the base material 1 without activation of 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 adhesive layer 5 and functional layer 3 is guaranteed.
  • the coating of the cylinder bore in particular the layer system in the form of a gradual transition and / or a gradient be designed, in particular in the chemical composition and / or the structural design. In this way, there is actually only one layer with a gradually changing composition and / or morphology, ie a gradual layer, in particular a gradual layer system.
  • a gradual layer in particular a gradual layer system, can thus be understood as meaning that the gradual layer directly at the first interface then comprises material which forms a chemical bond with the surface of the base material of the cylinder, ie in particular the material of the adhesion layer, ie interface material. As the distance from this surface increases, ie as the layer thickness increases, the layer material then gradually changes into the layer material of the protective thermally sprayed layer to be applied, preferably the functional layer.
  • the gradual layer in particular the graded layer system, with the gradually changing composition, ie the gradual transition and / or the gradient, comprise the following two variants:
  • the interface material gradually enters the material of the functional layer
  • Interfacial material wherein the interface material may comprise 60% by weight of molybdenum and 40% by weight of further element, preferably the interfacial material may consist of 60% by weight of molybdenum and 40% by weight of ⁇ 5 ⁇ . End of the layer with the gradually changing composition with 100 wt .-% functional layer share and 0 wt .-% fraction of interfacial material, so that the end of the gradual layer, at least partially forms the mantle surface of the bore of the cylinder and can act as a functional layer.
  • the interface material may comprise molybdenum and the further element, in particular consist of this, wherein the further element preferably the material of
  • Functional layer can correspond, and the interface material is gradually into the material of the functional layer, in particular the adhesive layer in the functional layer, where:
  • variant 2 can then have the following chemical composition and the following course:
  • Example 1
  • the proportion of the interface material on the gradual layer with the gradually changing composition from the start to the end preferably linearly or exponentially decrease, especially in the variant 1 and / or variant 2, and / or the proportion of the functional layer on the Layer with the gradually changing composition may preferably increase linearly or exponentially from start to finish, in particular in 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 form a chemical bond with the surface of the base material of the cylinder, that is to say in particular the material of the adhesion layer.
  • the layer material then gradually changes into the layer material of the protective thermally sprayed layer to be applied.
  • This could be realized, for example, via a double injection with a time-decreasing injection of the adhesive layer and / or a time-increasing injection of the functional layer.
  • 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 realized by a single injection, wherein two separate feeds for the Material of the adhesive layer and the functional layer can be used, in particular two powder conveyors, which are brought together in a Y-shaped component.
  • the interface material molybdenum and ⁇ 5 ⁇ include, preferably made of molybdenum and ⁇ 5 ⁇ .
  • Table 1 shows the average tensile strength achieved with conventional known activation (mechanical, corundum) and an interface material consisting of molybdenum and ⁇ 5 ⁇ , in particular, the interface material can also molybdenum and ⁇ 5 ⁇ and a proportion of impurities in the range of 0.1 to 0.3 wt. -% consist.
  • Table 1 Comparison of the bond tensile strengths with conventional known activation and with an interface material consisting of molybdenum and ⁇ 5 ⁇ .
  • FIG. 1 shows the prior art
  • Figure 2 shows a first embodiment of the present invention
  • Figure 3 shows a second embodiment of the present invention.
  • the example relates to the invention according to the first embodiment.
  • the bore of a cylinder is coated with the base material of the cylinder being an aluminum alloy and the bore having a diameter of 85 mm and the bore being 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) having a thickness of 200-300 microns.
  • the coating method of thermal spraying is to use atmospheric plasma spraying (APS).
  • powdered coating material is continuously brought to melt in a plasma, liquid atomized and then applied to the base material of the cylinder inside 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 uniformly charged with coating.
  • a 5-150 micron adhesive layer 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, for example, ionic nature are formed, and at the interface of the adhesive layer to the layer material, ionic bonds also occur and, in addition, mechanical entanglement through the rough sprayed layer.
  • sufficient adhesion is ensured at both interfaces.

Landscapes

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

Abstract

The invention relates to a cylinder of a piston-type internal combustion engine, wherein the cylinder comprises at least one bore with an inner lateral surface that is formed from a base material, wherein, in the region of the bore, the base material is at least partially provided with a system of layers and thus a first boundary surface is formed between the base material and the system of layers, and the system of layers comprises at least one thermally sprayed layer and the thermally sprayed layer at least partially forms the lateral surface of the bore and can act there as a functional layer, and wherein the first boundary surface does not comprise any profiling provided for the mechanical activation of the surface apart from the surface roughness that is produced by the production of the bore. The invention is characterized in that the material of the system of layers in the region of the boundary surface with respect to the base material, referred to hereinafter as the boundary surface material, comprises molybdenum and a further element and is connected to the base material by way of a chemical bond, and the boundary surface material differs from the material of the functional layer in the composition and/or structure thereof.

Description

Zylinderbohrungen beschichten ohne vorgängige Aktivierung der Oberfläche  Cylinder bores coat without prior activation of the surface
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. The cylinder bores of some piston internal combustion engines are usually provided with a coating by means of thermal spraying in order to minimize the weight and / or the friction and / or the wear. As a result, the fuel and oil consumption is reduced and preferably made the surface of the cylinder bore corrosion resistant.
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 is in danger of bursting 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 activation ensures that a mechanical entanglement between layer and base material of the cylinder block is produced, i. it comes to a positive conclusion. This pre-machining step of activating the cylinder tread 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 between layer and base material of the cylinder block achieved by the activation improves the adhesion of the layer to the base material and contributes to a long service life of the cylinder. Different techniques can be used to perform the activation. For example, the surface can be roughened by means of corundum jets, 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 of activation is to provide the surface with a profiling with undercuts, for example by means of machining. For example, here the dovetail geometry is used with advantage.
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. Accordingly, Figure 1 shows the mechanical entanglement of the sprayed layer 3 with the base material 1 by activation of the base material before coating. As a result, according to the prior art, the adhesion on the base material 1, for example a cylinder bore, is improved.
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 methods described above have, inter alia, the disadvantage that they can only be realized with increased production costs. 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 that carries out 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. 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. 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 12 beziehen sich auf weitere vorteilhafte Ausgestaltungen der vorliegenden Erfindung und Ansprüche 13 und 14 beziehen sich auf den entsprechenden Motor beziehungsweise dessen Herstellung. 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. There have been early attempts to avoid surface activation by means of an intermediate layer. For example, Shepard in US 2588422 discloses a molybdenum layer as an intermediate layer. This then forms on the one hand with the base material and on the other hand with the sprayed functional layer in each case an interface. Apart from the fact that elemental molybdenum is a very soft material, this approach also has the problem that it is not possible to satisfactorily improve the adhesion at both interfaces in an unsatisfactory manner. The present invention is therefore based on the object of specifying a method which allows the thermally sprayed layer to be applied to the casing of a cylinder bore in an adhesive manner without requiring activation, in particular mechanical activation, of the surface to be coated. According to the invention the object is achieved by the inventive cylinder according to claims 1 and the inventive method according to claim 8. Claims 2 to 7 and 9 to 12 relate to further advantageous embodiments of the present invention and claims 13 and 14 relate to the corresponding motor or its manufacture. The cylinder comprises at least one bore with an inner jacket which is formed from a base material, wherein in the region of the bore the base material is at least partially provided with a layer system. In this case, a first boundary surface is formed between the base material and the layer system, wherein the first boundary surface, apart from the surface roughness created by the production of the bore, does not include any profiling applied for activating the surface, in particular does not include any profiling applied for the mechanical activation of 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 layer sprayed 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 method is the application of an adhesive layer directly to the base material of the cylinder bore casing, wherein the adhesive layer forms a chemical compound at least with the base material. The adhesive layer may comprise the interface material, in particular consist of the interface material. The adhesive layer may be composed of the interface material. As a result, the adhesion at the interface to the base material is thus not achieved decisively by mechanical interlocking but essentially by 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 may in particular also consist essentially of molybdenum and at least one further element, in particular the interface material may consist of molybdenum and at least one further element. If in the present description or in the claims the presence of a further element is mentioned, this may or may not be present in elemental form but may 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 on the interface material, in particular on the adhesive layer, in a range of 30 to 90 wt .-% are and the Proportion of the further element on the interface material, in particular on the adhesive layer, in a range of 70 to 10 wt .-%, Favor the proportion of molybdenum on the interface material in a range of 40 to 80 wt .-% and the proportion of the other element on Interfacial material in a range of 60 to 20 wt .-%, more preferably the proportion of molybdenum on the interface material in a range of 50 to 70 wt .-% and the proportion of the further element in the interface material in a range of 50 to 30 wt. -% lie. Specifically, the content of molybdenum in the interface material may be in a range of 55 to 65% by weight or 58 to 62% by weight or 60% by weight, and the proportion of the other element in the interface material may be in the range of 45 to 35% by weight or from 42 to 38% by weight or at 40% by weight. lie. The interfacial material may also comprise a proportion of impurities, for example S and P in the range of 0.01 to 0.2 wt .-%, preferably 0.01 to 0.1 wt .-%.
In Ausgestaltung der Erfindung kann das weitere Element und/oder die Funktionsschicht die folgenden Materialien umfassen, insbesondere aus den folgenden Materialien bestehen: In an embodiment of the invention, the further element and / or the functional layer may comprise the following materials, in particular consisting of the following materials:
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: For the further element and / or the functional layer, a material, preferably an iron-based material (also referred to below 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 bis 1,5 Gewichts-% C = 0.4 to 1.5% by weight
Cr = 0,2 bis 2,5 Gewichts-%  Cr = 0.2 to 2.5% by weight
Mn = 0,2 bis 3 Gewichts-%  Mn = 0.2 to 3% by weight
Fe = Differenz auf 100 Gewichts-%,  Fe = difference to 100% by weight,
insbesondere kann das Pulver zusätzlich enthalten: In particular, the powder may additionally contain:
S = 0,01 bis 0,2 Gewichts-% S = 0.01 to 0.2% by weight
P = 0,01 bis 0,1 Gewichts-%.  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 Preferably, for the further element and / or the functional layer, the Fe base in the form of a powder, in particular a gas-atomized powder of the following chemical
Zusammensetzung eingesetzt werden:  Composition to be used:
C = 0,1 bis 0,8 Gewichts-% C = 0.1 to 0.8% by weight
Cr = 11 bis 18 Gewichts-%  Cr = 11 to 18% by weight
Mn = 0,1 bis 1,5 Gewichts-%  Mn = 0.1 to 1.5% by weight
Mo = 0,1 bis 5 Gewichts-%  Mo = 0.1 to 5% by weight
Fe = Differenz auf 100 Gewichts-%,  Fe = difference to 100% by weight,
insbesondere kann das Pulver zusätzlich enthalten: In particular, the powder may additionally contain:
S = 0,01 bis 0,2 Gewichts-%  S = 0.01 to 0.2% by weight
P = 0,01 bis 0,1 Gewichts-%.  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 FeO.2Cl.4Crl.4Mn, insbesondere auch Mo = 0,1 bis 5 Gew.-% enthalten. Die Partikelgrösse des Pulvers des weiteren Elements und/oder der Funktionsschicht kann im Bereich von 5 bis 25 μιη oder 10 bis 45 μιη oder 15 bis 60 μιη liegen. However, the further element and / or the functional layer can also be a Fe-base material with the following chemical composition FeO.2Cl.4Crl.4Mn, in particular also contain Mo = 0.1 to 5 wt .-%. The particle size of the powder of the further element and / or the functional layer may 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: However, the further element and / or the functional layer may also comprise the following materials, in particular consisting of the following materials:
• Fe-Base + 30% Mo - im Speziellen FeO.2Cl.4Crl.4Mn + 30% Mo Fe-base + 30% Mo - in particular FeO.2Cl.4Crl.4Mn + 30% Mo
• MMC=Metal Matrix Composite aus Fe-Base und einer Oxydkeramik, insbesondere einer tribologischen Oxydkeramik, bevorzugt eine Oxydkeramik die aus Ti02 oder aus ΑΙ203ΤΪ02- und/oder AI203Zr02- und/oder AI2O3-20ZrO2-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 Fel4Cr2Mo und 5 bis 50 Gew.-%, bevorzugt 35 Gew.-% der Oxydkeramik sein. MMC = metal matrix composite of Fe base and an oxide ceramic, in particular a tribological oxide ceramic, preferably an oxide ceramic consisting of TiO 2 or of ΑΙ203ΤΪ02 and / or Al 2 O 3 ZrO 2 and / or Al 2 O 3 20ZrO 2 alloy systems, and / or the proportion of Oxydkeramik in the material used, in particular powder, 5 to 50 wt .-%, preferably 35 wt .-% is. Specifically, the MMC may be Fel4Cr2Mo and 5 to 50 wt%, preferably 35 wt%, of the oxide ceramic.
• Vollkeramiken wie Ti02 oder Cr203 • all-ceramics like Ti02 or Cr203
• Cr3C2-25NiCr, insbesondere Cr3C2-25NiCr und 20% Mo  Cr3C2-25NiCr, especially Cr3C2-25NiCr and 20% Mo
• AISi und eine Keramik (wie Bsp. Ti02, Zn02), insbesondere AISi und 20 Gew.-% Mo und eine Keramik.  • AISi and a ceramic (such as Ti02, Zn02), in particular AISi and 20 wt .-% 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 in the present description or in the claims of an adhesive layer, for example within a layer system is mentioned, it does not necessarily have to be formed with a well-defined interface to the one or more other layers of the layer system, unless otherwise defined. For example, it may transition to another layer via a composition gradient, or may lack a well-defined layer due to interfacial 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 in the present description or in the claims the presence of a chemical element is mentioned, this need not be in elemental form but may 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 chosen so that this material also enters into a chemical compound with the material of the thermally sprayed functional layer to be applied and thus adheres.
Gemäss einer weiteren, ebenfalls bevorzugten zweiten Ausführungsform wird die Haftschicht so ausgestaltet, dass sie eine Oberflächenrauheit aufweist, welche dazu führt dass die aufzubringende thermisch gespritzte Funktionsschicht zumindest mechanisch auf der Haftschicht in ausreichendem Masse haftet. Beispielsweise kann eine entsprechende Rauheit durch gezielt kolumnares Wachstum erreicht werden. Es ist auch möglich die Rauheit der Haftschicht mittels erhöhter Porosität zu erreichen. According to a further, likewise preferred second embodiment, the adhesive layer is designed such that it has a surface roughness which results in the thermally sprayed functional layer to be applied adhering at least mechanically to the adhesive layer to a sufficient extent. For example, a corresponding roughness can be achieved by targeted columnar growth. It is also possible to achieve the roughness of the adhesive layer 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. 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. FIG. 2 shows an embodiment according to the invention according to which the adhesion of the sprayed functional layer 3 to the base material 1 without activation of 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 adhesive layer 5 and functional layer 3 is guaranteed. In an embodiment, the coating of the cylinder bore, in particular the layer system in the form of a gradual transition and / or a gradient be designed, in particular in the chemical composition and / or the structural design. In this way, there is actually only one layer with a gradually changing composition and / or morphology, ie a gradual layer, in particular a gradual layer system. A gradual layer, in particular a gradual layer system, can thus be understood as meaning that the gradual layer directly at the first interface then comprises material which forms a chemical bond with the surface of the base material of the cylinder, ie in particular the material of the adhesion layer, ie interface material. As the distance from this surface increases, ie as the layer thickness increases, the layer material then gradually changes into the layer material of the protective thermally sprayed layer 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 graded layer system, with the gradually changing composition, ie the gradual transition and / or the gradient, comprise the following two variants:
Variante 1 version 1
Das Grenzflächenmaterial geht graduell in das Material der funktionalen Schicht,  The interface material gradually enters the material of the functional layer,
insbesondere in die Funktionsschicht, über, wobei gilt: in particular into the functional layer, via, where:
Start der Schicht mit der graduell sich ändernden Zusammensetzung an der ersten Start the layer with the gradually changing composition at the first
Grenzfläche mit 0 Gew.-% Material der Funktionsschicht und 100 Gew.-% Interface with 0% by weight of functional layer material and 100% by weight
Grenzflächenmaterial, wobei das Grenzflächenmaterial 60 Gew.-% Molybdän und 40 Gew.-% weiteres Element umfassen kann, bevorzugt das Grenzflächenmaterial aus 60% Gew.-% Molybdän und 40 Gew.-% ΝΪ5ΑΙ 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. Interfacial material wherein the interface material may comprise 60% by weight of molybdenum and 40% by weight of further element, preferably the interfacial material may consist of 60% by weight of molybdenum and 40% by weight of ΝΪ5ΑΙ. End of the layer with the gradually changing composition with 100 wt .-% functional layer share and 0 wt .-% fraction of interfacial material, so that the end of the gradual layer, at least partially forms the mantle surface of the bore of the cylinder and can act as a functional layer.
Variante 2 Variant 2
Das Grenzflächenmaterial kann Molybdän und das weitere Element umfassen, insbesondere aus diesem bestehen, wobei das weitere Element bevorzugt dem Material der The interface material may comprise molybdenum and the further element, in particular consist of this, wherein the further element preferably the material of
Funktionsschicht entsprechen kann, und das Grenzflächenmaterial geht graduell in das Material der Funktionsschicht über, insbesondere die Haftschicht in die Funktionsschicht über, wobei gilt: Functional layer can correspond, and the interface material is gradually into the material of the functional layer, in particular the adhesive layer in the functional layer, where:
Start der Schicht mit der graduell sich ändernden Zusammensetzung an der ersten Start the layer with the gradually changing composition at the first
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. Boundary surface with 40 wt .-% proportion of further element and 50 to 70 wt .-%, preferably 60 wt .-% molybdenum. End of the layer with the gradually changing composition with 0 to 40 wt .-% proportion of molybdenum and 60 to 100 wt .-% proportion of further element, which corresponds in particular to the material of the functional layer, preferably 20 to 40 wt .-% proportion of molybdenum and 60 to 80 wt .-% proportion of further element, more preferably 30 wt .-% of molybdenum and 70 wt .-% share of further element, so that the end of gradual layer, at least partially forms the inner circumferential 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: Beispiel 1: For example, variant 2 can then have the following chemical composition and the following course: Example 1
Weiteres Element=Fe-Base, insbesondere Funktionsschicht=weiteres Element=Fe-Base Start: Fe-Base und 60 Gew.-% Molybdän, bevorzugt FeO.2Cl.4Crl.4Mn + 60% Mo Ende: Fe-Base, bevorzugt FeO.2Cl.4Crl.4Mn  Further element = Fe base, in particular functional layer = further element = Fe base Start: Fe base and 60% by weight molybdenum, preferably FeO.2Cl.4Crl.4Mn + 60% Mo end: Fe base, preferably FeO. 2Cl.4Crl.4Mn
Beispiel 2: Example 2:
Weiteres Element=Fe-Base, insbesondere Funktionsschicht=weiteres Element=Fe-Base Start: Fe-Base und 60 Gew.-% Molybdän, bevorzugt FeO.2Cl.4Crl.4Mn + 60% Molybdän Ende: Fe-Base und 30 Gew.-% Molybdän, bevorzugt FeO.2Cl.4Crl.4Mn + 30% Molybdän  Further element = Fe base, in particular functional layer = further element = Fe base Start: Fe base and 60% by weight molybdenum, preferably FeO.2Cl.4Crl.4Mn + 60% molybdenum end: Fe base and 30% by weight -% molybdenum, preferably FeO.2Cl.4Crl.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 on the gradual layer with the gradually changing composition from the start to the end preferably linearly or exponentially decrease, especially in the variant 1 and / or variant 2, and / or the proportion of the functional layer on the Layer with the gradually changing composition may preferably increase linearly or exponentially from start to finish, in particular in 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 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 form a chemical bond with the surface of the base material of the cylinder, that is to say in particular the material of the adhesion layer. With increasing distance from this
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.  Surface, i. As the layer thickness increases, the layer material then gradually changes into the layer material of the protective thermally sprayed layer to be applied. This could be realized, for example, via a double injection with a time-decreasing injection of the adhesive layer and / or a time-increasing injection of the functional layer. In this way, there is actually only one layer with a gradually changing composition and / or morphology, ie 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 realized by a single injection, wherein two separate feeds for the Material of the adhesive layer and the functional layer can be used, in particular two powder conveyors, 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. In Ausgestaltung der Erfindung kann das Grenzflächenmaterial Molybdän und ΝΪ5ΑΙ umfassen, bevorzugt aus Molybdän und ΝΪ5ΑΙ bestehen. Die folgende Tabelle 1 zeigt die durchschnittlich erreichten Haftzugfestigkeiten bei herkömmlicher bekannter Aktivierung (mechanisch, Korund) und bei einem Grenzflächenmaterial bestehend aus Molybdän und ΝΪ5ΑΙ, insbesondere kann das Grenzflächenmaterial auch aus Molybdän und ΝΪ5ΑΙ und einem Anteil an Verunreinigungen im Bereich von 0.1 bis 0.3 Gew.-% bestehen. As an example of such an adhesive layer, a material composition comprising NiAl and Mo can be given. In an embodiment of the invention, the interface material molybdenum and ΝΪ5ΑΙ include, preferably made of molybdenum and ΝΪ5ΑΙ. The following Table 1 shows the average tensile strength achieved with conventional known activation (mechanical, corundum) and an interface material consisting of molybdenum and ΝΪ5ΑΙ, in particular, the interface material can also molybdenum and ΝΪ5ΑΙ and a proportion of impurities in the range of 0.1 to 0.3 wt. -% consist.
Tabelle 1: Vergleich der Haftzugfestigkeiten bei herkömmlicher bekannter Aktivierung und bei einem Grenzflächenmaterial bestehend aus Molybdän und ΝΪ5ΑΙ.  Table 1: Comparison of the bond tensile strengths with conventional known activation and with an interface material consisting of molybdenum and ΝΪ5ΑΙ.
Die Erfindung wird nun mit anhand eines Beispiels und mit Hilfe der Figuren im Detail dargestellt. The invention will now be illustrated in detail by way of example and with the aid of the figures.
Figur 1 zeigt den bisherigen Stand der Technik FIG. 1 shows the prior art
Figur 2 zeigt ein erstes Ausführungsbeispiel der vorliegenden Erfindung Figur 3 zeigt ein zweites Ausführungsbeispiel der vorliegenden Erfindung. 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, l%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. Figure 2 shows a first embodiment of the present invention Figure 3 shows a second embodiment of the present invention. The example relates to the invention according to the first embodiment. The bore of a cylinder is coated with the base material of the cylinder being an aluminum alloy and the bore having a diameter of 85 mm and the bore being 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) having a thickness of 200-300 microns. The coating method of thermal spraying is to use atmospheric plasma spraying (APS). Here, while supplying energy and process gases powdered coating material is continuously brought to melt in a plasma, liquid atomized and then applied to the base material of the cylinder inside 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 uniformly charged with coating.
Würde diese Schicht mittels der beschriebenen Methode einfach direkt auf das Grundmaterial aufgebracht, so würde diese nicht ausreichend auf dem Grundmateria l 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 by the method described, it would not adhere adequately to the base material. According to the prior 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, according to the invention, in the present example, a 5-150 micron adhesive layer 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. Thus, at the interface to the base material, chemical compounds of, for example, ionic nature are formed, and at the interface of the adhesive layer to the layer material, ionic bonds also occur and, in addition, mechanical entanglement through the rough sprayed layer. As a result, sufficient adhesion is ensured at both interfaces.

Claims

Ansprüche claims
1. Zylinder eines Kolben-Verbrennungsmotors, wobei der Zylinder zumindest eine Bohrung mit innerem Mantel der aus einem Grundmaterial gebildet wird umfasst, wobei im Bereich der Bohrung das Grundmaterial zumindest teilweise mit einem Schichtsystem versehen ist und so zwischen Grundmaterial und Schichtsystem eine erste Grenzfläche gebildet wird und das Schichtsystem zumindest eine thermisch gespritzte Schicht umfasst und die thermisch gespritzte Schicht zumindest teilweise die Manteloberfläche der Bohrung bildet und dort als funktionale Schicht wirken kann und wobei die erste Grenzfläche abgesehen von der durch die Herstellung der Bohrung entstandene Oberflächenrauigkeit keine zur Aktivierung der Oberfläche angebrachte Profilierung umfasst dadurch gekennzeichnet dass das Material des Schichtsystems im Bereich der Grenzfläche zum Grundmaterial, im Folgenden Grenzflächenmaterial genannt, Molybdän und mindestens ein weiteres Element umfasst und mit dem Grundmaterial über eine chemische Bindung verbunden ist und das Grenzflächenmaterial sich vom Material der funktionalen Schicht in seiner Zusammensetzung und/oder Struktur unterscheidet. 1. Cylinder of a piston 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 thus between the base material and the layer system, a first interface is formed and the layer system comprises at least one thermally sprayed layer and the thermally sprayed layer at least partially forms the mantle surface of the bore where it can act as a functional layer and wherein the first interface, apart from the surface roughness resulting from the production of the bore, does not have any profiling applied to activate the surface characterized in that the material of the layer system in the region of the interface to the base material, hereinafter referred to as interfacial material, molybdenum and at least one further element comprises and with the base material via a chem is bonded and the interfacial material is different from the material of the functional layer in its composition and / or structure.
2. Zylinder nach Anspruch 1, dadurch gekennzeichnet dass innerhalb des Schichtsystems strukturelle Mittel zum Zusammenhalt des Schichtsystems vorgesehen sind. 2. Cylinder according to claim 1, characterized in that structural means for cohesion of the layer system are provided within the layer system.
3. Zylinder nach Anspruch 2, dadurch gekennzeichnet, dass die strukturellen Mittel chemische Bindungen und/oder Grenzflächenrauigkeiten die vorzugsweise durch den Applikationsprozess des Grenzflächenmaterials entstanden sind und/oder durch einen graduellen Übergang von Grenzflächenmaterial zum Material der funktionalen Schicht, umfassen. 3. Cylinder according to claim 2, characterized in that the structural means comprise chemical bonds and / or boundary surface roughnesses which are preferably produced by the application process of the interface material and / or by a gradual transition of interface material to the material of the functional layer.
4. Zylinder nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die chemische Bindung Grenzflächenmaterial an das Grundmaterial durch ionische Bindungen und/oder durch kovalente Bindungen realisiert ist. 4. Cylinder according to one of claims 1 to 3, characterized in that the chemical bonding interface material is realized to the base material by ionic bonds and / or by covalent bonds.
5. Zylinder nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, das im Grenzflächenmaterial zumindest ein chemisches Element vorhanden ist welches mit einem chemischen Element im Grundmaterial übereinstimmt. 5. Cylinder according to one of claims 1 to 4, characterized in that in the interface material at least one chemical element is present which coincides with a chemical element in the base material.
6. Zylinder nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Schichtsystem über die Schichtdicke ausgehend von der ersten Grenzfläche hin zur durch die funktionale Schicht an der Manteloberfläche in der chemischen Zusammensetzung und/oder strukturellen Aufbau zumindest teilweise mindestens einen Gradienten bildet. 6. Cylinder according to one of the preceding claims, characterized in that the layer system at least partially forms at least one gradient over the layer thickness, starting from the first interface to the through the functional layer on the mantle surface in the chemical composition and / or structural design.
7. Zylinder nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass im Grenzflächenmaterial zumindest ein chemisches Element vorhanden ist welches mit einem chemischen Element in der funktionalen Schicht übereinstimmt. 7. Cylinder according to one of the preceding claims, characterized in that in the interface material at least one chemical element is present which coincides with a chemical element in the functional layer.
8. Verfahren zur Herstellung eines Zylinders für einen Kolben-Verbrennungsmotor mit Bohrung, wobei das Verfahren folgende Schritte umfasst: - Bereitstellen eines Zylinders mit Bohrung, wobei der innere Mantel der Bohrung aus einem Grundmaterial gebildet wird und deren Oberfläche ausser der durch die Herstellung der Bohrung entstandene Oberflächenrauigkeit keine Profilierung zur Aktivierung der Oberfläche umfasst. 8. A method of manufacturing a cylinder for a piston 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 of a Base material is formed and the surface except for the surface roughness resulting from the production of the bore does not comprise profiling to activate the surface.
- Beaufschlagung des inneren Mantels der Bohrung mit einem Schichtsystem welches an der Grenzfläche zum Grundmaterial ein Grenzflächenmaterial umfasst und wobei zumindest die die Oberfläche des Zylinderloches bildende Schicht des Schichtsystems thermisch gespritzt wird und eine funktionale Schicht bildet, - Applying to the inner shell of the bore with a layer system which comprises at the interface to the base material, an interface material and wherein at least the surface of the cylinder hole forming layer of the layer system is thermally sprayed and forms a functional layer,
dadurch gekennzeichnet, dass das Grenzflächenmaterial Molybdän und mindestens ein weiteres Element umfasst und so gewählt wird, dass es mit dem Grundmaterial eine chemische Bindung eingeht und das Schichtsystem derart aufgebracht wird, dass sich Grenzflächenmaterial und Material der funktionalen Schicht chemisch in der Zusammensetzung und/oder in der Struktur unterscheiden. characterized in that the interfacial material comprises molybdenum and at least one further element and is chosen such that it chemically binds with the base material and the layer system is applied such that interface material and material of the functional layer chemically in the composition and / or in different from the structure.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass der das Grenzflächenmateria l umfassende Bereich zwischen Grundmaterial und funktionaler Schicht als zur funktionalen Schicht eine zweite Grenzfläche bildende Grundschicht hergestellt wird, und zwar dergestalt dass die zweite Grenzfläche zur mechanischen Aktivierung geeignete Strukturen wie zum Beispiel Porosität und/oder Rauigkeit und oder Kolumnarität aufweist. 9. Method according to claim 8, characterized in that the region between the base material and the functional layer which comprises the interfacial material is produced as a base layer forming a second interface for the functional layer, in such a way that the second interface for mechanical activation has suitable structures, such as, for example, porosity and / or roughness and or columnarity.
10. Verfahren nach einem der Ansprüche 8 und 9, dadurch gekennzeichnet, dass das Schichtsystem vollständig mittels thermischem Spritzen aufgebracht wird. 10. The method according to any one of claims 8 and 9, characterized in that the layer system is completely applied by means of thermal spraying.
11. Verfahren nach einem der Ansprüche 8 und 10, dadurch gekennzeichnet, dass das Schichtsystem in Richtung Schichtdicke zumindest teilweise als Gradientenschicht ausgebildet ist. 11. The method according to any one of claims 8 and 10, characterized in that the layer system is at least partially formed in the direction of layer thickness as a gradient layer.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass das Schichtsystem der Übergang vom Grenzflächenmaterial zum Material der funktionalen Schicht als Gradient ausgebildet wird. 12. The method according to claim 11, characterized in that the layer system, the transition from the interface material to the material of the functional layer is formed as a gradient.
13. Motor mit einem Zylinder nach einem der Ansprüche 1 bis 7 13. Motor with a cylinder according to one of claims 1 to 7
14. Verfahren zur Herstellung eines Motors, dadurch gekennzeichnet, dass das Verfahren die Verfahrensschritte nach einem der Ansprüche 8 bis 12 umfasst. 14. A method for producing a motor, characterized in that the method comprises the method steps according to one of claims 8 to 12.
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)

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PCT/EP2017/067748 WO2018011362A1 (en) 2016-07-13 2017-07-13 Coating cylinder bores without prior activation of the surface

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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

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CN109642306A (en) 2019-04-16
US20190292644A1 (en) 2019-09-26
US10920308B2 (en) 2021-02-16
JP2022191217A (en) 2022-12-27
JP7166243B2 (en) 2022-11-07
JP2019524997A (en) 2019-09-05
WO2018011362A1 (en) 2018-01-18

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