EP1161569B1 - Method and system for producing wear-resistant surfaces - Google Patents
Method and system for producing wear-resistant surfaces Download PDFInfo
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- EP1161569B1 EP1161569B1 EP00902632A EP00902632A EP1161569B1 EP 1161569 B1 EP1161569 B1 EP 1161569B1 EP 00902632 A EP00902632 A EP 00902632A EP 00902632 A EP00902632 A EP 00902632A EP 1161569 B1 EP1161569 B1 EP 1161569B1
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- cooling
- thermally conductive
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- crankcase
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
- C23C4/16—Wires; Tubes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
Definitions
- the invention relates to a method for producing wear-resistant surfaces Components made of an Al-Si alloy, the wear-resistant surfaces using a thermal spraying, in particular flame spraying, plasma spraying or HV spraying, or a laser beam is applied, according to the preamble of claim 1.
- the invention further relates to an arrangement for producing wear-resistant surfaces on components made of an Al-Si alloy, in particular on cylinder running surfaces of Cylinders of a crankcase of a reciprocating internal combustion engine, according to the Preamble of claim 11.
- hypoeutectic aluminum-silicon alloys mainly used for cylinder crankcases are unsuitable for the tribological loading of the piston-piston ring-cylinder raceway system due to the low proportion of the wear-resistant silicon phase.
- Hypereutectic alloys such as the AlSil 7 Cu 4 Mg alloy, have a sufficient proportion of silicon crystallites.
- This hard, wear-resistant structural component is highlighted by chemical and / or mechanical processing steps compared to the matrix consisting of the aluminum mixed crystal and forms a required wing portion.
- the castability, the poor machinability and the high cost of this alloy are disadvantageous compared to the hypoeutectic and nearutectic alloys.
- sub- and near-eutectic alloys are made of galvanic Coatings applied directly to the raceways.
- this is expensive and Insufficiently stable tribochemically.
- thermal Spray layers which are also applied directly to the tread. The However, the adhesive strength of these layers is due to a sole micromechanical Insufficient brackets.
- the present invention has for its object an improved method of above type and an improved arrangement of the above.
- the formation of the wear-resistant surface in the form of a thermal spray layer are additionally processed with a laser beam, in particular remelted.
- remelting, alloying, Dispersing and / or coating by means of a laser beam or by thermal Spraying performed.
- the component is a crankcase of a reciprocating piston internal combustion engine
- the coating is carried out on the cylinder running surfaces of cylinders.
- the heat-conducting device comprises at least a cooling plate with channels for a cooling medium, which to the crankcase be created at least on one side, on which there are open ends of the cylinders.
- the heat-conducting device comprises at least one cooling mandrel corresponding to the cross section of the cylinder, which in axial direction of the cylinder following a coating zone and / or the Coating zone is subsequently brought into contact with the cylinder running surface.
- the thermally conductive device comprises Coolant tank, in which the crankcase during the manufacture of the wear-resistant surface is immersed in such a way that a cooling medium level in the Cylinder is located below a coating zone in the direction of gravity.
- a cooling medium level in the Cylinder is located below a coating zone in the direction of gravity.
- the active cooling of the heat-conducting device is expediently carried out with a Gas, nitrogen and / or a coolant performed.
- a heat-conducting device which in heat-conducting Contact is arranged with the component and comprises a cooling medium.
- the cooling medium expediently comprises a gas, nitrogen and / or Cooling liquid, which with a high heat capacity coefficient for one ensure high heat dissipation.
- the heat-conducting device comprises at least a cooling plate which has channels flowed through by the cooling medium, one Cooling plate is arranged on the crankcase on at least one side on which the End cylinder open.
- the cooling plate is for good heat dissipation on the circumference of the cylinder bore formed in such a ring that they have a corresponding cylinder bore lies flush against the circumferential edge of the same.
- the thermally conductive comprises Device at least one corresponding to the cross section of a cylinder bore Cooling mandrel with channels flowed through by the cooling medium, which in the axial direction of the Cylinder is arranged on one or both sides of a coating zone such that a thermally conductive contact between the cooling mandrel and the cylinder running surface is.
- Cooling mandrel formed a catch nose.
- the cooling mandrel is on its Circumferential cylinder surface facing formed with cooling bristles, which in brush contact with the cylinder surface.
- Cooling bristles made of a heat-conducting material, in particular copper.
- the heat-conducting device comprises at least one cooling medium pool, in which the component can be immersed in such a way that a cooling medium level a predetermined distance from a coating zone having.
- the preferred embodiment shown in Fig. 1 of an inventive Arrangement comprises a coating device 10, which by means of a Plasma beam 12, which is for example a laser beam, has a cylinder running surface 14 a cylinder wall 15 of a cylinder 16 of a crankcase 18 coated.
- the Coating device 10 is rotatable about a longitudinal axis 20, as with arrow 22 indicated, and displaceable along the longitudinal axis 20, as indicated by arrow 24.
- the crankcase 18 has a water space 26 for a cooling medium.
- Through the Rotation and translation movement of the coating device 10 relative to Cylinder wall 15 is the cylinder running surface 14 in predetermined areas editable.
- a current work area of the Coating device 10 in which the plasma beam 12 or a laser beam onto the Cylinder running surface 14 meets referred to as the machining zone 28.
- the arrangement comprises a cooling plate 30 which is built, i.e. by means of Plate system or mechanically, or cast and includes cooling channels 32, which are flowed through by the cooling medium.
- the Cooling channels have, for example, a rectangular and / or round cross section and are in particular above a contact surface 34 between cooling plate 30 and Cylinder wall 15 formed.
- a cooling plate 30 is either on one side or on both sides the open ends of the cylinder 16.
- the cooling plates corresponding to the cylinder cross-section formed so that they are on the circumferential cylinder wall 15 and an opening in the ring Introduce the coating device 10 available.
- the in Fig. 1st lower cooling plate 30 has the further advantage in an annular design that Process gases and excess coating material, which at the Cylinder track 14 is not melted or does not adhere in the direction of gravity 1 can be discharged downwards.
- the arrangement further comprises a cooling mandrel 36, which is designed according to the cross section of the cylinder 16 such that this Cooling mandrel 36 can be inserted into the cylinder 16 and there in the circumferential direction Cylinder wall 15 is present.
- a cooling mandrel 36 which is designed according to the cross section of the cylinder 16 such that this Cooling mandrel 36 can be inserted into the cylinder 16 and there in the circumferential direction Cylinder wall 15 is present.
- cooling bristles 38 on the jacket of the cooling mandrel 36 for example made of copper, provided with the surface of the cylinder wall 15 are in contact and in this way heat from the cylinder wall 15 to Derive cooling dome 36.
- a cooling medium also flows through in the cooling mandrel Cooling channels 40 are provided, which for active cooling and in the aforementioned manner Serve heat energy dissipation.
- the cooling channels are spiraling educated.
- a catch basin 42 formed on the lower cooling mandrel 36 in FIG. 1 15 particles adhering to the cylinder wall are not collected.
- the collecting basin 42 is expediently also filled with cooling medium.
- a additional collecting nose 44 guides excess, falling Coating material in the catch basin 42.
- For the cooling medium in the Collecting basin 42 and / or in the cooling channels 40 is a cooling medium inflow 46 and Coolant drain 48 provided.
- honing after the Coating take place, the honing process depending on the desired surface quality can consist of several steps.
- FIG. 2 is a heat conductive Device provided in the form of a cooling medium basin 52, in which the Crankcase 18 is immersed.
- a tracking of the immersion (arrow 58) such that a cooling medium level 54 always a constant, predetermined distance 56 from for example 20 mm from the coating zone 28. So there is a Heat dissipation by immersion cooling of the crankcase 18.
- a cooling fluid such as gas, nitrogen or a coolant is passed, which for further cooling of the Cylinder wall 15 leads and thus additional heat from the coating zone dissipates.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cylinder Crankcases Of Internal Combustion Engines (AREA)
- Coating By Spraying Or Casting (AREA)
Description
Die Erfindung betrifft ein Verfahren zum Herstellen verschleißfester Oberflächen an Bauteilen aus einer Al-Si-Legierung, wobei die verschleißfeste Oberflächen mittels eines thermischen Spritzens, insbesondere Flammspritzen, Plasmaspritzen oder HV-Spritzen, oder eines Laserstrahles aufgebracht wird, gemäß dem Oberbegriff des Anspruchs 1. Die Erfindung betrifft ferner eine Anordnung zum Herstellen verschleißfester Oberflächen an Bauteilen aus einer Al-Si-Legierung, insbesondere an Zylinderlaufflächen von Zylindern eines Kurbelgehäuses einer Hubkolben-Brennkraftmaschine, gemäß dem Oberbegriff des Anspruchs 11.The invention relates to a method for producing wear-resistant surfaces Components made of an Al-Si alloy, the wear-resistant surfaces using a thermal spraying, in particular flame spraying, plasma spraying or HV spraying, or a laser beam is applied, according to the preamble of claim 1. The invention further relates to an arrangement for producing wear-resistant surfaces on components made of an Al-Si alloy, in particular on cylinder running surfaces of Cylinders of a crankcase of a reciprocating internal combustion engine, according to the Preamble of claim 11.
Die für Zylinderkurbelgehäuse vorwiegend eingesetzten untereutektischen Aluminium-Silizium-Legierungen sind aufgrund des zu geringen Anteils der verschleißfesten Siliziumphase für die tribologische Beanspruchung des Systems Kolben-Kolbenring-Zylinderlaufbahn ungeeignet. Übereutektische Legierungen, z.B. die Legierung AlSil7Cu4Mg besitzen einen ausreichenden Anteil an Siliziumkristalliten. Dieser harte, verschleißbeständige Gefügebestandteil wird durch chemische und/oder mechanische Bearbeitungsstufen gegenüber der aus dem Aluminiummischkristall bestehenden Matrix hervorgehoben und bildet einen erforderlichen Tragflächenanteil. Nachteilig wirkt sich jedoch die gegenüber den untereutektischen und naheutektischen Legierungen mangelhafte Vergießbarkeit, die schlechte Bearbeitbarkeit und die hohen Kosten für diese Legierung aus.The hypoeutectic aluminum-silicon alloys mainly used for cylinder crankcases are unsuitable for the tribological loading of the piston-piston ring-cylinder raceway system due to the low proportion of the wear-resistant silicon phase. Hypereutectic alloys, such as the AlSil 7 Cu 4 Mg alloy, have a sufficient proportion of silicon crystallites. This hard, wear-resistant structural component is highlighted by chemical and / or mechanical processing steps compared to the matrix consisting of the aluminum mixed crystal and forms a required wing portion. However, the castability, the poor machinability and the high cost of this alloy are disadvantageous compared to the hypoeutectic and nearutectic alloys.
Eine Möglichkeit zur Umgehung dieses Nachteils ist das Eingießen von Laufbuchsen aus verschleißbeständigem Material wie z.B. Grauguß- und übereutektischen Aluminiumlegierungen. Problematisch ist hier jedoch die Verbindung zwischen Buchse und Umguß, welcher alleine durch eine mechanische Verzahnung gewährleistet wird. Durch Einsatz eines porösen keramischen Buchsenwerkstoffs ist es möglich, beim Gießprozeß diesen zu infiltrieren und zu einer stofflichen Verbindung zu gelangen. Dazu ist eine langsame Formfüllung sowie die Anwendung von hohem Druck erforderlich, was die Wirtschaftlichkeit des Verfahrens erheblich herabsetzt.One way to circumvent this disadvantage is to cast bushings from wear-resistant material such as Cast iron and hypereutectic Aluminum alloys. However, the connection between the socket is problematic here and casting, which is guaranteed solely by a mechanical toothing. By using a porous ceramic bushing material, it is possible to Casting process to infiltrate this and to reach a material connection. To slow mold filling as well as the application of high pressure is required significantly reduces the economics of the process.
Alternativ werden unter- und naheutektischen Legierungen der galvanische Beschichtungen direkt auf die Laufbahnen aufgebracht. Dies ist jedoch teuer und tribochemisch nur ungenügend beständig. Eine weitere Alternative bilden thermische Spritzschichten, welche ebenfalls direkt auf die Laufflächen appliziert werden. Die Haftfestigkeit dieser Schichten ist jedoch aufgrund einer alleinigen mikromechanischen Verklammerung nur ungenügend.Alternatively, sub- and near-eutectic alloys are made of galvanic Coatings applied directly to the raceways. However, this is expensive and Insufficiently stable tribochemically. Another alternative is thermal Spray layers, which are also applied directly to the tread. The However, the adhesive strength of these layers is due to a sole micromechanical Insufficient brackets.
Es wurde daher bereits vorgeschlagen, die Oberflächenmodifikationen Umschmelzen. Einlegieren, Dispergieren und Beschichten durch den Einsatz eines Lasers auszuführen, wie beispielsweise aus der DE 196 43 029 A1 bekannt. Hierbei es ist erforderlich, die durch die Laserstrahlen in das Kurbelgehäuse bzw. die Zylinderlaufflächen eingebrachte Energie ausreichend schnell abzuführen. Ein zu hoher Wärmeeintrag bei energiereichen Laserstrahlen kann nämlich zu unerwünschten Gefügeveränderungen im Kurbelgehäuse führen. Hierzu wird von der DE 196 43 029 A1 bereits vorgeschlagen, die Bauteiloberfläche über Kühlwasserkanäle des Kurbelgehäuses zu kühlen.It has therefore already been proposed to remelt the surface modifications. Alloying, dispersing and coating using a laser, as known for example from DE 196 43 029 A1. This requires that introduced by the laser beams into the crankcase or the cylinder surfaces To dissipate energy quickly enough. Too high heat input in high energy Laser beams can cause undesirable structural changes in the crankcase to lead. For this purpose, DE 196 43 029 A1 has already proposed that Cool component surface via cooling water channels of the crankcase.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein verbessertes Verfahren der obengenannten Art sowie eine verbesserte Anordnung der o.g. Art zur Verfügung zu stellen, welche eine Beschichtung von Bauteilen auch mit hochenergetischen Beschichtungsvorrichtungen, wie beispielsweise leistungsstarken Lasern, ohne thermisch bedingte Veränderungen des Werkstoffes des Bauteiles erlaubt.The present invention has for its object an improved method of above type and an improved arrangement of the above. Kind of available too make a coating of components even with high-energy Coating devices, such as powerful lasers, without thermal changes in the material of the component allowed.
Diese Aufgabe wird erfindungsgemäß durch ein Verfahren der o.g. Art mit den in Anspruch 1 gekennzeichneten Merkmalen und durch eine Anordnung der o.g. Art mit den in Anspruch 11 gekennzeichneten Merkmalen gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind in den abhängigen Ansprüchen angegeben.This object is achieved by a method of the above. Kind of with the in Characteristic characterized in claim 1 and by an arrangement of the above. Kind with solved the features characterized in claim 11. Advantageous configurations the invention are specified in the dependent claims.
Bei einem Verfahren der o.g. Art ist es erfindungsgemäß vorgesehen, daß während der Herstellung der verschleißfesten Oberfläche wenigstens eine wärmeleitende Vorrichtung in wärmeleitenden Berührungskontakt mit dem Bauteil gebracht und diese wärmeleitende Vorrichtung aktiv gekühlt wird.In a procedure of the above Art is provided according to the invention that during the Production of the wear-resistant surface at least one heat-conducting device brought into thermally conductive contact with the component and this thermally conductive Device is actively cooled.
Dies hat den Vorteil, daß eine gute Wärmeabführung mit erhöhter Kühlleistung während des Beschichtungsvorganges zur Verfügung steht, so daß insbesondere ein Lasereinlegieren und Laserbeschichten ohne die Gefahr einer wärmebedingten Strukturveränderung im Werkstoff des Kurbelgehäuses ausgeführt werden kann. Hierdurch ist es möglich, auch mit höheren Energien zu beschichten, so daß beispielsweise eine höhere Eindringtiefe des Beschichtungswerkstoffes in den Werkstoff des Bauteiles, eine bessere Verbindung zwischen der Beschichtung und dem Werkstoff des Bauteiles und/oder eine höhere Schichtdicke erzielt wird.This has the advantage that good heat dissipation with increased cooling performance during the coating process is available, so that in particular a Laser alloying and laser coating without the risk of heat-related Structural change in the material of the crankcase can be carried out. This makes it possible to coat with higher energies, so that for example a greater depth of penetration of the coating material into the material of the component, a better connection between the coating and the material of the component and / or a higher layer thickness is achieved.
Zum weiteren Verbessern von Eigenschaften der aufgebrachten Beschichtung wird nach dem Ausbilden der verschleißfesten Oberfläche in Form einer thermischen Spritzschicht diese zusätzlich mit einem Laserstrahl bearbeitet, insbesondere umgeschmolzen.To further improve properties of the applied coating, the formation of the wear-resistant surface in the form of a thermal spray layer these are additionally processed with a laser beam, in particular remelted.
In einer bevorzugten Ausführungsform wird daß ein Umschmelzen, Einlegieren, Dispergieren und/oder Beschichten mittels eines Laserstrahles oder durch thermisches Spritzen durchgeführt.In a preferred embodiment, remelting, alloying, Dispersing and / or coating by means of a laser beam or by thermal Spraying performed.
Beispielsweise ist das Bauteil ein Kurbelgehäuse einer Hubkolben-Brennkraftmaschinen, an dessen Zylinderlaufflächen von Zylindern die Beschichtung durchgeführt wird. Hierbei wird in einer bevorzugten Ausführungsform während der Herstellung der verschleißfesten Oberfläche ein Wasserraum des Kurbelgehäuses mit einem Kühlmedium, insbesondere Gas, Stickstoff oder einer Kühlflüssigkeit, durchströmt.For example, the component is a crankcase of a reciprocating piston internal combustion engine, the coating is carried out on the cylinder running surfaces of cylinders. in this connection is in a preferred embodiment during the manufacture of the wear-resistant surface a water space of the crankcase with a Cooling medium, in particular gas, nitrogen or a cooling liquid flows through.
In einer alternativen Ausführungsform umfaßt die wärmeleitende Vorrichtung wenigstens eine Kühlplatte mit Kanälen für ein Kühlmedium, welche an das Kurbelgehäuse an wenigstens einer Seite angelegt werden, an der sich offene Enden der Zylinder befinden.In an alternative embodiment, the heat-conducting device comprises at least a cooling plate with channels for a cooling medium, which to the crankcase be created at least on one side, on which there are open ends of the cylinders.
In einer weiteren alternativen Ausführungsform umfaßt die wärmeleitende Vorrichtung wenigstens einen dem Querschnitt des Zylinders entsprechenden Kühldorn, welcher in axialer Richtung des Zylinders einer Beschichtungszone folgend und/oder der Beschichtungszone nacheilend mit der Zylinderlauffläche in Kontakt gebracht wird.In a further alternative embodiment, the heat-conducting device comprises at least one cooling mandrel corresponding to the cross section of the cylinder, which in axial direction of the cylinder following a coating zone and / or the Coating zone is subsequently brought into contact with the cylinder running surface.
In einer weiteren alternativen Ausführungsform umfaßt die wärmeleitende Vorrichtung ein Kühlmediumbecken, in welches das Kurbelgehäuse während der Herstellung der verschleißfesten Oberfläche derart eingetaucht wird, daß sich ein Kühlmediumspiegel im Zylinder in Schwerkraftrichtung unterhalb einer Beschichtungszone befindet. Hierbei wird eine Eintauchtiefe des Kurbelgehäuses in das Kühlmediumbecken derart nachgeführt, daß ein konstanter vorbestimmter Abstand zwischen der Beschichtungszone und dem Kühlmittelspiegel eingehalten wird.In a further alternative embodiment, the thermally conductive device comprises Coolant tank, in which the crankcase during the manufacture of the wear-resistant surface is immersed in such a way that a cooling medium level in the Cylinder is located below a coating zone in the direction of gravity. Here will tracked an immersion depth of the crankcase in the cooling medium basin, that a constant predetermined distance between the coating zone and the Coolant level is maintained.
Zweckmäßigerweise wird die aktive Kühlung der wärmeleitenden Vorrichtung mit einem Gas, Stickstoff und/oder einer Kühlflüssigkeit durchgeführt. The active cooling of the heat-conducting device is expediently carried out with a Gas, nitrogen and / or a coolant performed.
Bei einer Anordnung der o.g. Art ist es erfindungsgemäß vorgesehen, daß eine wärmeleitende Vorrichtung vorgesehen ist, welche in wärmeleitendem Berührungskontakt mit dem Bauteil angeordnet ist und ein Kühlmedium umfaßt.With an arrangement of the above Art is provided according to the invention that a heat-conducting device is provided, which in heat-conducting Contact is arranged with the component and comprises a cooling medium.
Dies hat den Vorteil, daß eine gute Wärmeabführung mit erhöhter Kühlleistung während des Beschichtungsvorganges zur Verfügung steht, so daß insbesondere ein Lasereinlegieren und Laserbeschichten ohne die Gefahr einer wärmebedingten Strukturveränderung im Werkstoff des Kurbelgehäuses ausgeführt werden kann. Hierdurch ist es möglich, auch mit höheren Energien zu beschichten, so daß beispielsweise eine höhere Eindringtiefe des Beschichtungswerkstoffes in den Werkstoff des Bauteiles, eine bessere Verbindung zwischen der Beschichtung und dem Werkstoff des Bauteiles und/oder eine höhere Schichtdicke erzielt wird.This has the advantage that good heat dissipation with increased cooling performance during the coating process is available, so that in particular a Laser alloying and laser coating without the risk of heat-related Structural change in the material of the crankcase can be carried out. This makes it possible to coat with higher energies, so that for example a greater depth of penetration of the coating material into the material of the component, a better connection between the coating and the material of the component and / or a higher layer thickness is achieved.
Zweckmäßigerweise umfaßt das Kühlmedium ein Gas, Stickstoff und/oder eine Kühlflüssigkeit, welche mit einem hohen Wärmekapazitätskoeffizienten für einen entsprechend hohen Wärmeabtransport sorgen.The cooling medium expediently comprises a gas, nitrogen and / or Cooling liquid, which with a high heat capacity coefficient for one ensure high heat dissipation.
In einer bevorzugten Ausführungsform umfaßt die wärmeleitende Vorrichtung wenigstens eine Kühlplatte, welche vom Kühlmedium durchströmte Kanäle aufweist, wobei eine Kühlplatte am Kurbelgehäuse an wenigstens einer Seite angeordnet ist, an der die Zylinder offen enden.In a preferred embodiment, the heat-conducting device comprises at least a cooling plate which has channels flowed through by the cooling medium, one Cooling plate is arranged on the crankcase on at least one side on which the End cylinder open.
Für einen guten Wärmeabtransport am Umfang der Zylinderbohrung ist die Kühlplatte derart ringförmig ausgebildet, daß sie mit einer entsprechenden Zylinderbohrung fluchtend am umlaufenden Rand derselben aufliegt.The cooling plate is for good heat dissipation on the circumference of the cylinder bore formed in such a ring that they have a corresponding cylinder bore lies flush against the circumferential edge of the same.
In einer alternativen bevorzugten Ausführungsform umfaßt die wärmeleitende Vorrichtung wenigstens einen dem Querschnitt einer Zylinderbohrung entsprechenden Kühldorn mit vom Kühlmedium durchströmten Kanälen, welcher in axialer Richtung des Zylinders ein- oder beidseitig einer Beschichtungszone derart angeordnet ist, daß ein wärmeleitender Kontakt zwischen dem Kühldorn mit der Zylinderlauffläche ausgebildet ist.In an alternative preferred embodiment, the thermally conductive comprises Device at least one corresponding to the cross section of a cylinder bore Cooling mandrel with channels flowed through by the cooling medium, which in the axial direction of the Cylinder is arranged on one or both sides of a coating zone such that a thermally conductive contact between the cooling mandrel and the cylinder running surface is.
Für eine hohe Kühlleistung nahe der Zylinderlauffläche sind die vom Kühlmedium durchströmten Kanäle spiralförmig umlaufend ausgebildet. For a high cooling capacity close to the cylinder surface, they are from the cooling medium flowed through channels formed spirally.
Zum Auffangen von überschüssigem Beschichtungsmaterial ist ein in Schwerkraftrichtung unterhalb der Beschichtungszone angeordneter Kühldorn mit einem Auffangbecken für überschüssiges Beschichtungsmaterial ausgebildet.To collect excess coating material, an in Direction of gravity below the coating zone arranged cooling mandrel with a Collection basin designed for excess coating material.
Zum Auffangen und Einleiten von überschüssigem Beschichtungsmaterial in das Auffangbecken ist an einer der Beschichtungszone zugewandten Seite des Umfangs des Kühldornes eine Auffangnase ausgebildet.For collecting and introducing excess coating material into the Collecting basin is on one side of the circumference of the coating zone Cooling mandrel formed a catch nose.
Zur Erhöhung einer Kühlwirkung des Kühldornes ist der Kühldorn an seinem der Zylinderlauffläche zugewandten Umfang mit Kühlborsten ausgebildet, welche in bürstendem Kontakt mit der Zylinderlauffläche stehen. Zweckmäßigerweise sind die Kühlborsten aus einem wärmeleitenden Material, insbesondere Kupfer, gefertigt.To increase a cooling effect of the cooling mandrel, the cooling mandrel is on its Circumferential cylinder surface facing formed with cooling bristles, which in brush contact with the cylinder surface. These are expediently Cooling bristles made of a heat-conducting material, in particular copper.
In einer weiteren alternativen Ausführungsform umfaßt die wärmeleitende Vorrichtung wenigstens ein Kühlmediumbecken, in welches das Bauteil derart eintauchbar ist, daß ein Kühlmediumspiegel einen vorbestimmten Abstand von einer Beschichtungszone aufweist.In a further alternative embodiment, the heat-conducting device comprises at least one cooling medium pool, in which the component can be immersed in such a way that a cooling medium level a predetermined distance from a coating zone having.
Besonders vorteilhaft ist es, an das erfindungsgemäße Beschichtungsverfahren einen Hon-Vorgang anzuschließen, um die beschichtete Oberfläche zu glätten.It is particularly advantageous to use the coating method according to the invention Connect honing process to smooth the coated surface.
Weitere Merkmale, Vorteile und vorteilhafte Ausgestaltungen der Erfindung ergeben sich aus den abhängigen Ansprüchen, sowie aus der nachstehenden Beschreibung der Erfindung anhand der beigefügten Zeichnungen. Diese zeigen in
- Fig. 1
- in einer Schnittansicht eine erste bevorzugte Ausführungsform einer erfindungsgemäßen Anordnung, welche drei bevorzugte Ausführungsformen einer zusätzlichen Kühlung verwirklicht.
- Fig. 2
- in einer Schnittansicht eine zweite bevorzugte Ausführungsform einer erfindungsgemäßen Anordnung.
- Fig. 1
- in a sectional view a first preferred embodiment of an arrangement according to the invention, which realizes three preferred embodiments of an additional cooling.
- Fig. 2
- in a sectional view a second preferred embodiment of an arrangement according to the invention.
Die in Fig. 1 dargestellte bevorzugte Ausführungsform einer erfindungsgemäßen
Anordnung umfaßt eine Beschichtungsvorrichtung 10, welche mittels eines
Plasmastrahles 12, welcher beispielsweise ein Laserstrahl ist, eine Zylinderlauffläche 14
einer Zylinderwand 15 eines Zylinders 16 eines Kurbelgehäuses 18 beschichtet. Die
Beschichtungsvorrichtung 10 ist um eine Längsachse 20 drehbar, wie mit Pfeil 22
angedeutet, und entlang der Längsachse 20 verschiebbar, wie mit Pfeil 24 angedeutet.
Das Kurbelgehäuse 18 weist einen Wasserraum 26 für ein Kühlmedium auf. Durch die
Rotations- und Translationsbewegung der Beschichtungsvorrichtung 10 relativ zur
Zylinderwandung 15 ist die Zylinderlauffläche 14 in vorbestimmten Bereichen
bearbeitbar. Hierbei ist nachfolgend ein aktueller Arbeitsbereich der
Beschichtungsvorrichtung 10, in dem der Plasmastrahl 12 oder ein Laserstrahl auf die
Zylinderlauffläche 14 trifft, als Bearbeitungszone 28 bezeichnet.The preferred embodiment shown in Fig. 1 of an inventive
Arrangement comprises a
Erfindungsgemäß umfaßt die Anordnung eine Kühlplatte 30, welche gebaut, d.h. mittels
Plattensystem oder mechanisch, oder gegossen gefertigt ist und Kühlkanäle 32 umfaßt,
welche von dem Kühlmedium durchflossen werden. Auf diese Weise ist die Kühlplatte
aktiv gekühlt und führt über die bloße Wärmeleitung hinaus aktiv Wärmeenergie ab. Die
Kühlkanäle weisen beispielsweise einen rechteckigen und/oder runden Querschnitt auf
und sind insbesondere oberhalb einer Kontaktfläche 34 zwischen Kühlplatte 30 und
Zylinderwandung 15 ausgebildet. Eine Kühlplatte 30 ist entweder einseitig oder beidseitig
der offenen Enden des Zylinders 16 angeordnet. Ferner sind die Kühlplatten
entsprechend dem Zylinderquerschnitt ringförmig ausgebildet so daß sie auf dem
umlaufenden Zylinderwandung 15 aufliegen und in dem Ring eine Öffnung zum
Einführen der Beschichtungsvorrichtung 10 zur Verfügung stellen. Die in der Fig. 1
unterer Kühlplatte 30 hat bei ringförmiger Ausführung den weiteren Vorteil, daß
Prozeßgase und überschüssiges Beschichtungsmaterial, welches an der
Zylinderlaufbahn 14 nicht angeschmolzen ist bzw. nicht anhaftet, in Schwerkraftrichtung
in der Fig. 1 nach unten abgeführt werden können.According to the invention the arrangement comprises a
Erfindungsgemäß umfaßt die Anordnung ferner einen Kühldorn 36, welcher
entsprechend dem Querschnitt des Zylinders 16 derart ausgebildet ist, daß dieser
Kühldorn 36 in den Zylinder 16 einführbar ist und dort in Umfangsrichtung an der
Zylinderwandung 15 anliegt. Alternativ oder zusätzlich zum Anliegen des Kühldornes 36
direkt an der Zylinderwandung 15 sind am Mantel des Kühldornes 36 Kühlborsten 38,
beispielsweise aus Kupfer, vorgesehen, welche mit der Oberfläche der Zylinderwandung
15 in Kontakt stehen und auf diese Weise Wärme von der Zylinderwandung 15 zum
Kühldom 36 ableiten. In dem Kühldorn sind ferner von einem Kühlmedium durchströmte
Kühlkanäle 40 vorgesehen, welche in der vorerwähnten Weise zur aktiven Kühlung und
Wärmeenergieabführung dienen. Die Kühlkanäle sind spiralförmig umlaufend
ausgebildet. According to the invention, the arrangement further comprises a cooling
Mittels eines am in der Fig. 1 unteren Kühldorn 36 ausgebildeten Auffangbeckes 42
werden nicht an der Zylinderwandung 15 haftende Partikel aufgefangen.
Zweckmäßigerweise ist auch das Auffangbecken 42 mit Kühlmedium gefüllt. Eine
zusätzliche Auffangnase 44 leitet überschüssigen, herabfallenden
Beschichtungswerkstoff in das Auffangbecken 42. Für das Kühlmedium in dem
Auffangbecken 42 und/oder in den Kühlkanälen 40 ist ein Kühlmediumzufluß 46 und ein
Kühlmediumabfluß 48 vorgesehen. Erfindungsgemäß wird ein oder werden beide der in
Fig. 1 dargestellten Kühldorne 36 in der Vorschubgeschwindigkeit der
Beschichtungsvorrichtung in Pfeilrichtung 24 mitgeführt, wie durch Pfeile 50 angedeutet.By means of a
Zur Glättung der beschichteten Oberfläche kann zudem ein Honen nach der Beschichtung erfolgen, wobei der Hon-Vorgang je nach gewünschter Oberflächengüte mehrere Schritte umfassen kann.To smooth the coated surface, honing after the Coating take place, the honing process depending on the desired surface quality can consist of several steps.
In einer weiteren alternativen Ausführungsform gemäß Fig. 2 ist eine wärmeleitende
Vorrichtung in Form eines Kühlmediumbeckens 52 vorgesehen, in welches das
Kurbelgehäuse 18 eingetaucht wird. Hierbei erfolgt gemäß dem Vorschub der
Beschichtungsvorrichtung 10 eine Nachführung des Eintauchens (Pfeil 58) derart, daß
ein Kühlmediumspiegel 54 immer einen konstanten, vorbestimmten Abstand 56 von
beispielsweise 20 mm von der Beschichtungszone 28 aufweist. Hierbei erfolgt also eine
Wärmeableitung durch eine Tauchkühlung des Kurbelgehäuses 18.In a further alternative embodiment according to FIG. 2 is a heat conductive
Device provided in the form of a cooling
Die drei vorgenannten Kühloptionen sind dabei erfindungsgemäß alternativ oder in beliebiger Kombination miteinander in einer einzigen erfindungsgemäßen Anordnung ausgebildet.The three aforementioned cooling options are alternative or in accordance with the invention any combination with each other in a single arrangement according to the invention educated.
In einer bevorzugten Weiterbildung der Erfindung ist es ferner vorgesehen, daß während
der Beschichtung der Zylinderlauffläche 14 mit dem Plasmastrahl 12 oder einem
Laserstrahl durch den Wasserraum 26 ein Kühlfluid, wie beispielsweise Gas, Stickstoff
oder eine Kühlflüssigkeit geleitet wird, welche zu einer weiteren Kühlung der
Zylinderwandung 15 führt und somit zusätzlich Wärme aus der Beschichtungszone
abführt.In a preferred development of the invention it is further provided that during
the coating of the
Claims (22)
- Process for producing wear-resistant surfaces on components made from an AlSi alloy, the wear-resistant surfaces being applied by means of thermal spraying or a laser beam, characterized in that during the production of the wear-resistant surface at least one thermally conductive device is brought into thermally conductive contact with the component, and this thermally conductive device is actively cooled.
- Process according to Claim 1, characterized in that, after the wear-resistant surface has been formed in the form of a thermally sprayed layer, this layer is additionally treated, in particular remelted, using a laser beam.
- Process according to Claim 1 or 2, characterized in that remelting, alloying, dispersing and/or coating is carried out by means of a laser beam or by thermal spraying.
- Process according to one of the preceding claims, characterized in that the component is a crankcase of a reciprocating internal combustion engine, on whose cylinder liners of cylinders the coating is carried out.
- Process according to Claim 4, characterized in that during the production of the wear-resistant surface a water chamber of the crankcase has a cooling medium, in particular gas, nitrogen or a cooling liquid, flowing through it.
- Process according to Claim 4 or 5, characterized in that the thermally conductive device comprises at least one cooling plate with passages for a cooling medium, which are applied to the crankcase on at least one side at which open ends of the cylinders are situated.
- Process according to one of Claims 4 to 6, characterized in that the thermally conductive device comprises at least one cooling mandrel which corresponds to the cross section of the cylinder and is brought into contact with the cylinder liner trailing a coating zone and/or following the coating zone, as seen in the axial direction of the cylinder.
- Process according to one of Claims 4 to 7, characterized in that the thermally conductive device comprises a cooling-medium tank, into which the crankcase is dipped during the production of the wear-resistant surface, in such a manner that a cooling-medium level in the cylinder is situated below a coating zone in the direction of the force of gravity.
- Process according to Claim 8, characterized in that a depth to which the crankcase is dipped into the cooling-medium tank is tracked in such a manner that a constant, predetermined distance is maintained between the coating zone and the cooling-medium level.
- Process according to one of the preceding claims, characterized in that the active cooling of the thermally conductive device is carried out using a gas, nitrogen and/or a cooling liquid.
- Arrangement for producing wear-resistant surfaces on components made from an AlSi alloy, in particular on cylinder liners (14) of cylinders (16) of a crankcase (18) of a reciprocating internal combustion engine, characterized in that a thermally conductive device (30, 36, 52) is provided, which is arranged in thermally conductive contact with the component (16) and comprises a cooling medium.
- Arrangement according to Claim 11, characterized in that the cooling medium comprises a gas, nitrogen and/or a cooling liquid.
- Arrangement according to Claim 11 or 12, characterized in that the thermally conductive device has at least one cooling plate (30), which has passages (32) through which the cooling medium flows, a cooling plate (30) being arranged on the crankcase (18), on at least one side at which the cylinders (16) are open at the end.
- Arrangement according to Claim 13, characterized in that the cooling plate (30) is of annular design, in such a manner that it rests on the circumferential edge of a corresponding cylinder bore (16), aligned with said bore.
- Arrangement according to one of Claims 11 to 14, characterized in that the thermally conductive device comprises at least one cooling mandrel (36) which corresponds to the cross section of a cylinder bore (16), has passages (40) through which the cooling medium flows and, in the axial direction of the cylinder (16), is arranged on one or both sides of a coating zone (28), in such a manner that thermally conductive contact is formed between the cooling mandrel (36) and the cylinder liner (14).
- Arrangement according to Claim 15, characterized in that the passages (40) through which the cooling medium flows are of helically encircling design.
- Arrangement according to Claim 15 or 16, characterized in that a cooling mandrel (36), which is arranged beneath the coating zone (28) in the direction of the force of gravity, is designed with a collection tank (42) for excess coating material.
- Arrangement according to Claim 17, characterized in that a collection lug (44) is formed on a side of the periphery of the cooling mandrel (36) which faces the coating zone (28).
- Arrangement according to one of Claims 15 to 18, characterized in that the cooling mandrel (36), on its periphery which faces the cylinder liner (14), is designed with cooling bristles (38) which are in brushing contact with the cylinder liner (14).
- Arrangement according to Claim 19, characterized in that the cooling bristles (38) are made from a thermally conductive material, in particular copper.
- Arrangement according to one of Claims 11 to 20, characterized in that the thermally conductive device comprises at least one cooling-medium tank (52), into which the component (18) can be dipped in such a manner that a cooling-medium level (54) is at a predetermined distance (56) from a coating zone.
- Process according to Claim 1, characterized in that a honing operation on the surface follows the thermal surface treatment of the component.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19907104 | 1999-02-19 | ||
DE19907104 | 1999-02-19 | ||
DE19941562A DE19941562A1 (en) | 1999-02-19 | 1999-09-01 | Method and arrangement for producing wear-resistant surfaces |
DE19941562 | 1999-09-01 | ||
PCT/EP2000/000575 WO2000049194A1 (en) | 1999-02-19 | 2000-01-26 | Method and system for producing wear-resistant surfaces |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1161569A1 EP1161569A1 (en) | 2001-12-12 |
EP1161569B1 true EP1161569B1 (en) | 2002-12-18 |
EP1161569B2 EP1161569B2 (en) | 2006-02-08 |
Family
ID=26051950
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00902632A Expired - Lifetime EP1161569B2 (en) | 1999-02-19 | 2000-01-26 | Method and system for producing wear-resistant surfaces |
Country Status (5)
Country | Link |
---|---|
US (1) | US6634179B2 (en) |
EP (1) | EP1161569B2 (en) |
JP (1) | JP2002537487A (en) |
CN (1) | CN1153844C (en) |
WO (1) | WO2000049194A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10313957A1 (en) * | 2002-06-27 | 2004-01-22 | Bwg Gmbh & Co. Kg | Method for coating a surface of a track component and track component |
DE102005005359B4 (en) * | 2005-02-02 | 2009-05-07 | Siemens Ag | Method for cold gas spraying |
DE102011106564A1 (en) * | 2011-07-05 | 2013-01-10 | Mahle International Gmbh | Method for producing a cylinder surface and cylinder liner |
WO2013077147A1 (en) * | 2011-11-22 | 2013-05-30 | 日産自動車株式会社 | Manufacturing method for cylinder block, and cylinder block |
WO2015068519A1 (en) * | 2013-11-05 | 2015-05-14 | 日産自動車株式会社 | Spray coating forming device and spray coating forming method |
CN105177567A (en) * | 2015-09-24 | 2015-12-23 | 安庆市灵宝机械有限责任公司 | Preparation method of wear-resistant coating on surface of steel base |
CN105331972A (en) * | 2015-09-24 | 2016-02-17 | 安庆市灵宝机械有限责任公司 | Method for manufacturing wear-resisting coating for wear-resisting coal cutting tooth |
CN105543838A (en) * | 2015-12-25 | 2016-05-04 | 燕山大学 | Remanufacturing method for marine crankshaft |
US11915850B2 (en) | 2017-12-20 | 2024-02-27 | Applied Materials, Inc. | Two channel cosine-theta coil assembly |
CN110735102B (en) * | 2019-11-15 | 2024-01-26 | 天宜上佳(天津)新材料有限公司 | Brake disc production method and brake disc cooling device |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE404764B (en) * | 1976-04-28 | 1978-10-30 | Volvo Penta Ab | FABRICS AND PROCEDURE AND CAST FORM FOR MANUFACTURE OF FABRICS |
US4175503A (en) * | 1976-12-22 | 1979-11-27 | Ford Motor Company | Method of making air engine housing |
DE2739356C2 (en) | 1977-09-01 | 1984-09-27 | Audi Nsu Auto Union Ag, 7107 Neckarsulm | Process for applying metal spray coatings to the inner surface of a hollow body |
JPS61231155A (en) | 1985-04-05 | 1986-10-15 | Yoshikawa Kogyo Kk | Method for thermally spraying to inner surface of sheet cylinder |
DE3715325A1 (en) † | 1987-05-08 | 1988-11-24 | Castolin Sa | METHOD FOR PRODUCING SLIDING SURFACES ON PARTS OF VEHICLE ENGINES |
DE3808285A1 (en) | 1988-03-12 | 1989-09-21 | Messer Griesheim Gmbh | Process for producing hard and wear-resistant surface layers |
DE3813802A1 (en) † | 1988-04-23 | 1989-11-09 | Glyco Metall Werke | LAYERING MATERIAL OR LAYERING MATERIAL WITH A FUNCTIONAL LAYER APPLIED ON A SUPPORT LAYER, IN PARTICULAR SLIDING LAYER WITH THE STRUCTURE OF A SOLID, BUT MELTABLE DISPERSION |
DE3922378A1 (en) † | 1989-07-07 | 1991-01-17 | Audi Ag | METHOD FOR PRODUCING WEAR-RESISTANT SURFACES ON COMPONENTS FROM AN ALUMINUM-SILICUM ALLOY |
JPH03173758A (en) | 1989-12-01 | 1991-07-29 | Mazda Motor Corp | Manufacture of sliding member |
JP2681302B2 (en) | 1990-02-13 | 1997-11-26 | 株式会社オティックス | Method and apparatus for thermal spraying of direct hit type valve lifter |
JPH0472051A (en) | 1990-07-11 | 1992-03-06 | Toyota Motor Corp | Formation of sprayed deposit on internal surface of cylinder bore of cylinder block |
JPH04358056A (en) | 1991-06-04 | 1992-12-11 | Toyota Motor Corp | Metal thermal-spraying method |
US5271967A (en) * | 1992-08-21 | 1993-12-21 | General Motors Corporation | Method and apparatus for application of thermal spray coatings to engine blocks |
US5795659A (en) * | 1992-09-05 | 1998-08-18 | International Inc. | Aluminide-silicide coatings coated products |
US5775402A (en) * | 1995-10-31 | 1998-07-07 | Massachusetts Institute Of Technology | Enhancement of thermal properties of tooling made by solid free form fabrication techniques |
JPH09151782A (en) * | 1995-11-29 | 1997-06-10 | Toyota Motor Corp | Manufacture of cylinder block |
DE19626175C2 (en) * | 1996-06-29 | 2000-01-13 | Honsel Ag | Method and device for producing a brake drum or a brake disc |
DE19643029A1 (en) * | 1996-10-18 | 1998-04-23 | Bayerische Motoren Werke Ag | Method for coating an internal combustion engine component made of an aluminum alloy with silicon |
DE19740205B4 (en) | 1997-09-12 | 2004-11-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for applying a coating by means of plasma spraying |
US6349681B1 (en) * | 2000-05-22 | 2002-02-26 | General Motors Corporation | Cylinder block for internal combustion engine |
-
2000
- 2000-01-26 CN CNB008040044A patent/CN1153844C/en not_active Expired - Fee Related
- 2000-01-26 EP EP00902632A patent/EP1161569B2/en not_active Expired - Lifetime
- 2000-01-26 WO PCT/EP2000/000575 patent/WO2000049194A1/en active IP Right Grant
- 2000-01-26 JP JP2000599916A patent/JP2002537487A/en active Pending
-
2001
- 2001-08-20 US US09/933,051 patent/US6634179B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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JP2002537487A (en) | 2002-11-05 |
US6634179B2 (en) | 2003-10-21 |
EP1161569A1 (en) | 2001-12-12 |
WO2000049194A1 (en) | 2000-08-24 |
US20020012753A1 (en) | 2002-01-31 |
CN1153844C (en) | 2004-06-16 |
EP1161569B2 (en) | 2006-02-08 |
CN1341156A (en) | 2002-03-20 |
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