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EP1304396A1 - Alloy powder for coating and coating process - Google Patents

Alloy powder for coating and coating process Download PDF

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Publication number
EP1304396A1
EP1304396A1 EP02019625A EP02019625A EP1304396A1 EP 1304396 A1 EP1304396 A1 EP 1304396A1 EP 02019625 A EP02019625 A EP 02019625A EP 02019625 A EP02019625 A EP 02019625A EP 1304396 A1 EP1304396 A1 EP 1304396A1
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EP
European Patent Office
Prior art keywords
alloy powder
coating
weight
aluminum
alloy
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
EP02019625A
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German (de)
French (fr)
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EP1304396B1 (en
Inventor
Markus Wittmann
Götz Mielsch
Nigel Dr. Stothard
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Bayerische Motoren Werke AG
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Bayerische Motoren Werke AG
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Publication of EP1304396A1 publication Critical patent/EP1304396A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate

Definitions

  • the invention relates to an alloy powder for coating an aluminum alloy in particular existing component, in particular the valve seat area of a cylinder head an internal combustion engine.
  • the invention relates to a method for coating such Component by means of a high-energy beam.
  • valve seat area in particular one made of an aluminum alloy existing cylinder head in particular with regard to strength, resilience and to optimize abrasion and wear resistance, it is known, accordingly use robust valve seat rings.
  • DE 197 describes 21 406 A1 a valve seat, which fits into an aluminum or aluminum cylinder head Aluminum alloy inserted and / or connected to it.
  • valve seat especially due to large temperature fluctuations over one wide range and the associated thermal expansion as well as the high Load is very critical, so you switched to instead of Valve seat rings a direct coating of the seat on the cylinder head make.
  • EP 843 022 A1 which relates to Process for forming a valve seat by means of thermal spray coating.
  • the object of the invention is to provide a coating material and a method to provide its application, thereby avoiding the aforementioned Disadvantages of a valve seat area with a particular hardness without a tendency to Cracking is provided.
  • the coating produced is said to be a good one Wear resistance at high temperatures, high hardness and strength, have good thermal conductivity and lubrication.
  • the alloy powder advantageously contains aluminum (Al) 10-70% by weight, in particular 20-50% by weight silicon (Si) and 5-50% by weight, in particular 10-40 wt .-% titanium (Ti), corresponding to the Si or Ti content the hardness within wide limits - for example up to over 550 HV with AlSi50Ti30 - is controllable without an increased tendency to form cracks.
  • the alloying element titanium is used to refine the grain from the Melt deposited silicon primary crystals, so that despite one high grain content small grain sizes are present.
  • the alloy powder also contains up to 25% by weight, in particular 1-15% by weight of nickel (Ni) and / or up to 20% by weight, in particular 1-10 wt .-% copper (Cu) contain.
  • a particular advantage results from the addition of high-temperature lubricants to the alloy powder, boron nitrite (BN), graphite, B 2 O 3 and / or Co / Cr 2 O 2 being present in a proportion by weight of up to 20%, in particular 5- 10% have shown to be very suitable.
  • boron nitrite (BN), graphite, B 2 O 3 and / or Co / Cr 2 O 2 being present in a proportion by weight of up to 20%, in particular 5- 10% have shown to be very suitable.
  • the pocket-like islands of lubricant continuously formed in the layer are exposed again and again due to operational wear, so that a permanent lubricating effect is achieved over the service life.
  • the alloy powder also contains hard material particles.
  • Fig. 1 shows a micrograph of an using an aluminum-silicon powder coated component made of an aluminum alloy.
  • This type of coating is used to technology in particular Wear resistance of an aluminum component through alloying or application of alloying elements in the area of the surface.
  • an aluminum-silicon powder which is applied / applied in the molten state is, with a very high addition of Si the cooling 1 with the structure shown.
  • The are clearly recognizable in the Aluminum basic structure 10 embedded rod / lamellar silicon crystals 12a, 12b, 12c.
  • the aim is to have a high concentration of these silicon crystals and their firm anchoring in the aluminum base structure 10. In the present high silicon concentration of approx. 60 wt.
  • the silicon particles form rod / lamellar with a size of up to several 100 ⁇ m. This causes a very disadvantageous material behavior.
  • the one coated in this way The area is very brittle and tends to crack.
  • a desired high Si content stands the disadvantageous formation of large, rod / lamella-like Towards silicon crystals.
  • FIG. 2 shows the structure produced of the alloy powder according to the invention
  • alloy powder contains in addition to the Base element aluminum has a very high silicon content of approx. 62% by weight as well approx. 20% by weight titanium.
  • a Metal alloy with the appropriate composition processed into powder if necessary, it can also be advantageous to mix different alloy powders Mix composition so that an alloy powder with the desired Composition arises.
  • Al-Ti phases form in the basic matrix.
  • the formation of high-melting Al-Ti phases such as Al 3 Ti, whose melting point is approximately 1,340 ° C., is particularly preferred.
  • Silicon particles 22 are embedded in this very robust basic matrix 20, wherein the alloying element titanium continues to cause grain refinement when they are separated from the melt.
  • the micrograph shown in FIG. 2 shows this basic matrix 20 with embedded silicon particles 22, the silicon particles 22 being finely dispersed in a size of only approximately 20 ⁇ m, in particular of 1 to 5 ⁇ m, in spite of the high silicon content of approximately 60% by weight.
  • the Si content can be increased significantly without the Si primary crystals forming from the melt becoming too large and rod-like / lamella-like.
  • the Control macro hardness - for example up to over 550 HV with AlSi50Ti30 - whereby nevertheless, an increased tendency to crack formation is avoided.
  • the addition of small amounts of nod (Ni) in the range from 1 to 15% has an advantageous effect.
  • Further wear resistance of the microstructure matrix can also be achieved by adding hard material particles.
  • SiC and / or B 4 C can be stored up to 30%, in particular 5 to 20%, by weight as a wear protection carrier.
  • B 4 C In conjunction with a fuel such as gas or hydrogen or in high-performance engines, B 4 C also takes on the role of a solid lubricant due to its oxidation to B 2 O 3 .
  • the coating takes place - as shown in Fig. 3 - by means of a coating lance 32, which has a feed 37 for the alloy powder and a light guide 33 for coupling a laser beam.
  • a diode laser is used as the laser or a solid-state laser such as Nd: YAG laser with an output of approx. 3 kW used.
  • the alloy powder is fed through the feed 37 of a nozzle 38 supplied, from which a powder jet 36 emerges; from the light guide 33 emerging laser beam is by means of several optical elements - schematically and exemplarily indicated with 34a, 34b - focused.
  • the Coating lance 32 is rotatable and / or displaceable relative to component 30, so that a targeted coating of the component 30 in regions is possible; if necessary the focus of the laser beam 35 and / or the nozzle 38 adjustable.
  • the alloy powder emerging from the nozzle 38 is sprayed in the direction of the component to be coated, it being at least partially melted by the heat of the laser beam.
  • the powder jet 36 is guided in the vicinity of or through the laser beam 35.
  • the powder jet emerges from the nozzle 38 in such a way that the required area is acted upon by the desired amount of alloy powder when it strikes the component surface 31a of the component 30 to be coated.
  • the focus 35a of the laser beam 35 is adjusted so that it lies exactly on the component surface; if the heating is too strong here, it can also be advantageous to guide the coating lance 32 in such a way that the component surface comes to lie above or below the focus 35a.
  • the energy density in the focal spot of the laser steel is approximately 10 4 W / cm 2 .
  • alloying takes place in the 1/10 mm area combined with an application of a few millimeters, approx. 2-3 mm, thick layer; that shown and described with Figure 2 In this way, the wear protection layer is firmly anchored in the base material.
  • the component - the cylinder head - expediently cooled This is a compromise between a quick Heat dissipation to prevent the melting of the Base material, between an ideal gradient to form the desired structure and between a slow cooling and slight Temperature differences to avoid cracks found.
  • the whole is done Coating process under a protective gas atmosphere such as argon or nitrogen.
  • a protective gas atmosphere such as argon or nitrogen.
  • the powder material is sprayed with protective gas, whereby the Shielding gas carried in the feed 37 or in a separate line to the Area of the nozzle 38 is passed.
  • alloy powder As an alternative to applying the alloy powder as described, this can be done Alloy powder also in the form of a paste for example coating area are applied.
  • the coating lance then includes only the laser device and possibly a protective gas supply device, which makes it structurally much simpler.
  • the cylinder head blank provided for coating is combined with a a certain allowance, so that subsequently possibly in the coating occurring heat distortion in the finishing can be compensated.
  • the valve seat areas to be coated are pre-processed with a certain undersize, since a layer is applied there. During the Coating of the valve seat area 31a, 31b, 31c, 31d moves the Coating lance 32 with a linear speed of up to 3 m / min and will rotated accordingly. There are several adjacent caterpillars - each after width one to two - with a degree of overlap of approx. 30-50% applied. Finally, the coated area is machined.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

Alloy powder for coating a component especially made of an aluminum alloy, especially the valve seat region of a cylinder head of an internal combustion engine, comprises aluminum, silicon, and titanium. <??>An Independent claim is also included for a process for coating a component using the above alloy powder and a high energy laser beam. <??>Preferred Features: The alloy powder contains in addition to the base element aluminum 10-70, especially 20-50 wt.% silicon and 5-50, especially 10-40 wt.% titanium. The alloy powder contains up to 25, especially 1-15 wt.% nickel and/or up to 20, especially 1-10 wt.% copper, a high temperature lubricant, preferably up to 20, especially 5-10 wt.% boron nitrite, graphite, boric oxide (B2O3) and/or cobalt/chromium oxide (Co/Cr2O2), and hard particles, preferably up to 30, especially 5-20 wt.% silicon carbide (SiC) and/or boron carbide (B4C).

Description

Die Erfindung betrifft gemäß dem Oberbegriff des Patentanspruchs 1 ein Legierungspulver zur Beschichtung eines insbesondere aus einer Aluminium-Legierung bestehenden Bauteiles, insbesondere des Ventilsitzbereiches eines Zylinderkopfes einer Brennkraftmaschine.According to the preamble of claim 1, the invention relates to an alloy powder for coating an aluminum alloy in particular existing component, in particular the valve seat area of a cylinder head an internal combustion engine.

Weiterhin bezieht sich die Erfindung auf ein Verfahren zur Beschichtung eines derartigen Bauteils mittels eines Hochenergiestrahles.Furthermore, the invention relates to a method for coating such Component by means of a high-energy beam.

Um den hochbelasteten Ventilsitzbereich eines insbesondere aus einer Aluminium-Legierung bestehenden Zylinderkopfes insbesondere hinsichtlich Festigkeit, Belastbarkeit und Abrieb- und Verschleißfestigkeit zu optimieren, ist es bekannt, entsprechend belastbare Ventilsitzringe einzusetzen. Beispielsweise beschreibt die DE 197 21 406 A1 einen Ventilsitz, welcher in einen Zylinderkopf aus Aluminium oder einer Aluminiumlegierung eingefügt und/oder mit diesen verbunden ist.Around the highly stressed valve seat area, in particular one made of an aluminum alloy existing cylinder head in particular with regard to strength, resilience and to optimize abrasion and wear resistance, it is known, accordingly use robust valve seat rings. For example, DE 197 describes 21 406 A1 a valve seat, which fits into an aluminum or aluminum cylinder head Aluminum alloy inserted and / or connected to it.

Es hat sich jedoch herausgestellt, dass die Verbindung zwischen Ventilsitz und Zylinderkopf insbesondere aufgrund großer Temperaturschwankungen über einen weiten Bereich und der damit einhergehenden Wärmeausdehnung sowie der hohen Belastung sehr kritisch ist, so dass man dazu übergegangen ist, anstelle von Ventilsitzringen eine direkte Beschichtung der Sitzfläche am Zylinderkopf vorzunehmen.However, it has been found that the connection between the valve seat and the cylinder head especially due to large temperature fluctuations over one wide range and the associated thermal expansion as well as the high Load is very critical, so you switched to instead of Valve seat rings a direct coating of the seat on the cylinder head make.

In diesem Zusammenhang wird auf die EP 843 022 A1 verwiesen, die sich auf ein Verfahren zur Bildung eines Ventilsitzes mittels thermischem Spritzbeschichten bezieht.In this connection, reference is made to EP 843 022 A1, which relates to Process for forming a valve seat by means of thermal spray coating.

Nach wie vor ist insbesondere der Wärmeübergang zwischen Zylinderkopf und Ventilsitz in Bezug auf die Hochtemperaturbetriebsfestigkeit sehr kritisch. Hinzu kommt eine sehr hohe Neigung der eingesetzten Ventilsitzmaterialien zur Rissbildung. Besonders schwer wiegen diese Nachteile bei Hochleistungsmotoren sowie bei Fahrzeugen, denen die Schmierwirkung des flüssigen Treibstoffes fehlt - wie beispielsweise bei Gas-/Wasserstofffahrzeugen- da hier besondere, extreme Belastungen bezüglich Temperatur und Verschleiß vorherrschen.In particular, the heat transfer between the cylinder head and Valve seat very critical in terms of high temperature durability. in addition there is a very high tendency of the valve seat materials used to crack. These disadvantages are particularly serious in high-performance engines as well in vehicles that lack the lubricating effect of the liquid fuel - such as For example with gas / hydrogen vehicles - because here special, extreme loads prevail in terms of temperature and wear.

Aufgabe der Erfindung ist es, einen Beschichtungswerkstoff sowie ein Verfahren zu dessen Aufbringung bereitzustellen, wodurch unter Vermeidung der genannten Nachteile ein Ventilsitzbereich mit einer besonderen Härte ohne Neigung zur Rissbildung bereitgestellt wird. Die erzeugte Beschichtung soll eine gute Verschleißbeständigkeit bei hohen Temperaturen, eine hohe Härte und Festigkeit, eine gute Wärmeleitfähigkeit und Schmierwirkung aufweisen.The object of the invention is to provide a coating material and a method to provide its application, thereby avoiding the aforementioned Disadvantages of a valve seat area with a particular hardness without a tendency to Cracking is provided. The coating produced is said to be a good one Wear resistance at high temperatures, high hardness and strength, have good thermal conductivity and lubrication.

Die Lösung der Aufgabe erfolgt gemäß den Merkmalen des Patentanspruchs 1 mittels eines Legierungspulvers zur Beschichtung, welches als wesentliche Bestandteile Aluminium (Al), Silizium (Si) und Titan (Ti) enthält.The object is achieved in accordance with the features of patent claim 1 by means of an alloy powder for coating, which is essential Contains components aluminum (Al), silicon (Si) and titanium (Ti).

Vorteilhafte Weiterbildungen des Legierungspulvers sind Gegenstand der Unteransprüche 2 bis 7.Advantageous further developments of the alloy powder are the subject of the subclaims 2 to 7.

Vorteilhaft enthält das Legierungspulver neben dem Basiselement Aluminium (Al) 10-70 gew.-%, insbesondere 20-50 gew.-% Silizium (Si) sowie 5-50 gew.-%, insbesondere 10-40 gew.-% Titan (Ti), wobei entsprechend dem Si- bzw. Ti-Anteil die Härte in weiten Grenzen - beispielsweise bis über 550 HV bei AlSi50Ti30 - steuerbar ist, ohne dass eine verstärkte Neigung zur Rissbildung auftritt. Darüber hinaus wird mit dem Legierungselement Titan eine Kornverfeinerung der aus der Schmelze abgeschiedenen Silizium-Primärkristalle erreicht, so dass trotz eines hohen Siliziumanteiles kleine Korngrößen vorliegen.In addition to the base element, the alloy powder advantageously contains aluminum (Al) 10-70% by weight, in particular 20-50% by weight silicon (Si) and 5-50% by weight, in particular 10-40 wt .-% titanium (Ti), corresponding to the Si or Ti content the hardness within wide limits - for example up to over 550 HV with AlSi50Ti30 - is controllable without an increased tendency to form cracks. About that In addition, the alloying element titanium is used to refine the grain from the Melt deposited silicon primary crystals, so that despite one high grain content small grain sizes are present.

Zweckmäßigerweise sind im Legierungspulver weiterhin bis zu 25 gew.-%, insbesondere 1-15 gew.-% Nickel (Ni) und/oder bis zu 20 gew.-%, insbesondere 1-10 gew.-% Kupfer (Cu) enthalten.Expediently, the alloy powder also contains up to 25% by weight, in particular 1-15% by weight of nickel (Ni) and / or up to 20% by weight, in particular 1-10 wt .-% copper (Cu) contain.

Ein besonderer Vorteil ergibt sich durch die Zugabe von Hochtemperaturschmierstoffen zum Legierungspulver, wobei sich Bornitrit (BN), Graphit, B2O3 und/oder Co/Cr2O2 in einer gewichtsanteiligen Menge von zusammen bis zu 20 %, insbesondere von 5-10 % als sehr geeignet herausgestellt haben. Die sich in der Schicht durchgehend bildenden taschenartigen Schmiermittelinseln werden aufgrund des betriebsbedingten Verschleißes immer wieder freigelegt, so dass über die Lebensdauer eine ständige Schmierwirkung erreicht wird.A particular advantage results from the addition of high-temperature lubricants to the alloy powder, boron nitrite (BN), graphite, B 2 O 3 and / or Co / Cr 2 O 2 being present in a proportion by weight of up to 20%, in particular 5- 10% have shown to be very suitable. The pocket-like islands of lubricant continuously formed in the layer are exposed again and again due to operational wear, so that a permanent lubricating effect is achieved over the service life.

Sehr von Vorteil ist es, wenn das Legierungspulver zudem Hartstoffpartikel enthält. Als besonders zweckmäßig hat sich in diesem Zusammenhang die Zugabe von SiC und/oder B4C gewichtsanteilig mit zusammen bis zu 30 gew.-%, insbesondere 5-20 % erwiesen.It is very advantageous if the alloy powder also contains hard material particles. In this context, the addition of SiC and / or B 4 C by weight together with up to 30% by weight, in particular 5-20%, has proven to be particularly expedient.

Mit den Unteransprüchen 8 bis 11 ist ein erfindungsgemäßes Verfahren unter Verwendung des beanspruchten Legierungspulvers angegeben.With sub-claims 8 to 11, a method according to the invention is under Use of the claimed alloy powder specified.

Nachfolgend wird ein besonders bevorzugtes Ausführungsbeispiel der Erfindung unter Bezugnahme auf Figuren näher beschrieben. Dabei zeigen

Fig. 1
ein Schliffbild eines Gefüges mit hohem Si-Anteil unter Verwendung eines herkömmlichen Legierungspulvers,
Fig. 2
ein Schliffbild eines Gefüges mit hohem Si-Anteil unter Verwendung des erfindungsgemäßen Legierungspulvers sowie
Fig. 3
schematisch und beispielhaft die Aufbringung des Legierungspulvers auf den Ventilsitzbereich eines Zylinderkopfes.
A particularly preferred exemplary embodiment of the invention is described in more detail below with reference to figures. Show
Fig. 1
a micrograph of a structure with a high Si content using a conventional alloy powder,
Fig. 2
a micrograph of a structure with a high Si content using the alloy powder according to the invention and
Fig. 3
schematically and exemplarily the application of the alloy powder to the valve seat area of a cylinder head.

Fig. 1 zeigt ein Schliffbild eines unter Verwendung eines Aluminium-Silizium-Pulvers beschichteten Bauteils aus einer Aluminiumlegierung. Gemäß dem Stand der Technik wird diese Art der Beschichtung verwendet, um insbesondere die Verschleißfestigkeit eines Aluminium-Bauteiles durch Einlegierung bzw. Aufbringung von Legierungselementen im Bereich der Oberfläche zu erhöhen. Verwendet wurde vorliegend ein Aluminium-Silizium-Pulver, welches in schmelzflüssigem Zustand ein-/aufgebracht wird, wobei bei einer sehr hohen Si-Beigabe sich bei Abkühlung das mit Fig. 1 gezeigte Gefüge ausbildet. Deutlich erkennbar sind die im Aluminiumgrundgefüge 10 eingebetteten stangen-/lamellenartigen Siliziumkristalle 12a, 12b, 12c. Angestrebt wird eine hohe Konzentration dieser Siliziumkristalle sowie deren feste Verankerung im Aluminiumgrundgefüge 10. Bei der vorliegenden hohen Siliziumkonzentration von ca. 60 gew. % bilden sich die Siliziumpartikel stangen-/lamellenartig mit einer Größe von bis zu mehreren 100 µm aus. Dies bedingt ein sehr nachteiliges Werkstoffverhalten. Der auf diese Weise beschichtete Bereich ist sehr spröde und neigt zur Rissbildung. Einem gewünschten hohen Si-Anteil steht die nachteilige Ausbildung großer, stangen-/lamellenartiger Siliziumkristalle entgegen.Fig. 1 shows a micrograph of an using an aluminum-silicon powder coated component made of an aluminum alloy. According to the state of the This type of coating is used to technology in particular Wear resistance of an aluminum component through alloying or application of alloying elements in the area of the surface. Was used in the present case an aluminum-silicon powder which is applied / applied in the molten state is, with a very high addition of Si the cooling 1 with the structure shown. The are clearly recognizable in the Aluminum basic structure 10 embedded rod / lamellar silicon crystals 12a, 12b, 12c. The aim is to have a high concentration of these silicon crystals and their firm anchoring in the aluminum base structure 10. In the present high silicon concentration of approx. 60 wt. % the silicon particles form rod / lamellar with a size of up to several 100 µm. This causes a very disadvantageous material behavior. The one coated in this way The area is very brittle and tends to crack. A desired high Si content stands the disadvantageous formation of large, rod / lamella-like Towards silicon crystals.

Ein Schliffbild eines mittels des erfindungsgemäßen Verfahrens unter Verwendung des erfindungsgemäßen Legierungspulvers erzeugten Gefüges zeigt Fig. 2. Das Legierungspulver enthält im vorliegenden Ausführungsbeispiel neben dem Basiselement Aluminium einen sehr hohen Siliziumanteil von ca. 62 gew.-% sowie ca. 20 gew.-% Titan. Zur Herstellung des Legierungspulvers wird eine Metalllegierung mit der entsprechenden Zusammensetzung zu Pulver verarbeitet, ggf. kann es auch vorteilhaft sein, Legierungspulver verschiedener Zusammensetzung zu mischen, so dass ein Legierungspulver mit der gewünschten Zusammensetzung entsteht.A micrograph of a using the method according to the invention FIG. 2 shows the structure produced of the alloy powder according to the invention In the present exemplary embodiment, alloy powder contains in addition to the Base element aluminum has a very high silicon content of approx. 62% by weight as well approx. 20% by weight titanium. To produce the alloy powder, a Metal alloy with the appropriate composition processed into powder, if necessary, it can also be advantageous to mix different alloy powders Mix composition so that an alloy powder with the desired Composition arises.

Unter Einfluss des Legierungselementes Titan (Ti) bilden sich in der Grundmatrix 20 Al-Ti-Phasen. Besonders bevorzugt wird die Ausbildung hochschmelzender Al-Ti-Phasen, wie beispielsweise Al3Ti, deren Schmelzpunkt bei ca. 1.340°C liegt. In dieser sehr robusten Grundmatrix 20 sind Siliziumpartikel 22 eingelagert, wobei das Legierungselement Titan weiterhin bei deren Abscheidung aus der Schmelze eine Kornverfeinerung bewirkt. Das in Fig. 2 gezeigte Schliffbild zeigt diese Grundmatrix 20 mit eingelagerten Siliziumpartikeln 22, wobei die Siliziumpartikel 22 trotz des hohen Siliziumanteils von ca. 60 Gew. % feinst dispersiert in einer Größe von nur ca. 20 µm insbesondere von 1 bis 5 um vorliegen. Der Si-Anteil kann stark angehoben werden, ohne dass die sich aus der Schmelze bildenden Si-Primärkristalle zu groß und stangen-/lamellenartiger werden.Under the influence of the alloy element titanium (Ti), 20 Al-Ti phases form in the basic matrix. The formation of high-melting Al-Ti phases, such as Al 3 Ti, whose melting point is approximately 1,340 ° C., is particularly preferred. Silicon particles 22 are embedded in this very robust basic matrix 20, wherein the alloying element titanium continues to cause grain refinement when they are separated from the melt. The micrograph shown in FIG. 2 shows this basic matrix 20 with embedded silicon particles 22, the silicon particles 22 being finely dispersed in a size of only approximately 20 μm, in particular of 1 to 5 μm, in spite of the high silicon content of approximately 60% by weight. The Si content can be increased significantly without the Si primary crystals forming from the melt becoming too large and rod-like / lamella-like.

Je nach Anteil Titan (Ti) und/oder Silizium (Si) lässt sich in breiten Grenzen die Macrohärte - beispielsweise bis über 550 HV bei AlSi50Ti30 - steuern, wobei dennoch eine verstärkte Neigung zur Rissbildung vermieden wird. Gegebenenfalls vorteilhaft wirkt sich Beigabe kleiner Mengen Nicken (Ni) im Bereich 1 bis 15 Gew. % und/oder Kupfer (Cu) im Bereich 1 bis 10 Gew. % aus.Depending on the proportion of titanium (Ti) and / or silicon (Si), the Control macro hardness - for example up to over 550 HV with AlSi50Ti30 - whereby nevertheless, an increased tendency to crack formation is avoided. Possibly The addition of small amounts of nod (Ni) in the range from 1 to 15% has an advantageous effect. % and / or copper (Cu) in the range 1 to 10% by weight.

Als sehr vorteilhaft hat es sich weiterhin herausgestellt, dem Legierungspulver einen Hochtemperaturschmierstoff wie beispielsweise Bornitrit (BN) beizugeben, wodurch der Einsatz in Hochleistungsmotoren und Gas-/Wasserstoffmotoren begünstigt wird. Dabei wird das Beschichtungspulver mit einem sehr feinen Bornitrit-Staub so aufbereitet, dass die Legierungspulverkörner vollständig von BN umhüllt werden. Zweckmäßig kann es gemäß eines weiteren Ausführungsbeispieles auch sein, einen zweiten Pulverturm bzw. eine zweite Pulverdüse zur gleichzeitigen Beförderung des Basislegierungspulvers und des BN vorzusehen und beide erst kurz vor/bei Aufbringung zu mischen.It has also proven to be very advantageous to unite the alloy powder Add high temperature lubricant such as boron nitride (BN), which use in high-performance engines and gas / hydrogen engines is favored. The coating powder with a very fine boron nitrite dust is like this processed so that the alloy powder grains are completely covered by BN. According to a further exemplary embodiment, it can also be expedient a second powder tower or a second powder nozzle for simultaneous conveyance of the base alloy powder and the BN and both only briefly mix before / during application.

Beim Erstarren der Schmelze nach dem Beschichten bilden sich in der Schicht kleine, als Schmiertaschen wirkende, aus Bornnitrit bestehende Inseln, welche bei betriebsbedingtem Verschleiß immer wieder freigelegt werden. Über die Lebensdauer der beschichteten Fläche wird so eine ständige Schmierwirkung erreicht. Ein Anteil von 5 bis 10 gew.-% ist in der Regel ausreichend, wobei ggf. bis zu 20 gew.-% BN beigemischt werden können. Auf gleiche Art und Weise können andere Hochtemperaturschmierstoffe - wie beispielsweise Graphit, B2O3 und/oder Co/Cr2O3 - dem Pulverwerkstoff zugegeben werden. When the melt solidifies after coating, small islands, which act as lubrication pockets and consist of boron nitride, form in the layer and are exposed again and again in the event of operational wear. A permanent lubrication effect is achieved over the life of the coated surface. A proportion of 5 to 10% by weight is generally sufficient, with up to 20% by weight BN possibly being added. In the same way, other high-temperature lubricants - such as graphite, B 2 O 3 and / or Co / Cr 2 O 3 - can be added to the powder material.

Eine weitere Verschleißbeständigkeit der Gefügematrix kann weiterhin durch Zugabe von Hartstoffpartikeln erreicht werden. Beispielsweise lässt sich SiC und/oder B4C als Verschleißschutzträger gewichtsanteilig bis zu 30 %, insbesondere 5 bis 20 %, einlagern. In Verbindung mit einem Kraftstoff wie Gas oder Wasserstoff bzw. bei Hochleistungsmotoren übernimmt B4C durch seine Oxidation zu B2O3 auch die Rolle eines Festschmierstoffes.Further wear resistance of the microstructure matrix can also be achieved by adding hard material particles. For example, SiC and / or B 4 C can be stored up to 30%, in particular 5 to 20%, by weight as a wear protection carrier. In conjunction with a fuel such as gas or hydrogen or in high-performance engines, B 4 C also takes on the role of a solid lubricant due to its oxidation to B 2 O 3 .

Die Beschichtung erfolgt - wie in Fig. 3 dargestellt - mittels einer Beschichtungslanze 32, welche eine Zuführung 37 für das Legierungspulver sowie einen Lichtleiter 33 zur Einkopplung eines Laserstrahles umfasst. Als Laser wird ein Diodenlaser oder ein Festkörperlaser wie Nd:YAG-Laser mit einer Leistung von ca. 3kW verwendet. Das Legierungspulver wird durch die Zuführung 37 einer Düse 38 zugeführt, aus der ein Pulverstrahl 36 austritt; der aus dem Lichtleiter 33 austretende Laserstrahl wird mittels einer mehrere optische Elemente - schematisch und beispielhaft mit 34a, 34b angedeutet - fokussiert. Die Beschichtungslanze 32 ist relativ zum Bauteil 30 drehbar und/oder verschieblich, so dass eine gezielte bereichsweise Beschichtung des Bauteiles 30 möglich ist; ggf. ist der Fokus des Laserstrahls 35 und/oder die Düse 38 verstellbar,.The coating takes place - as shown in Fig. 3 - by means of a coating lance 32, which has a feed 37 for the alloy powder and a light guide 33 for coupling a laser beam. A diode laser is used as the laser or a solid-state laser such as Nd: YAG laser with an output of approx. 3 kW used. The alloy powder is fed through the feed 37 of a nozzle 38 supplied, from which a powder jet 36 emerges; from the light guide 33 emerging laser beam is by means of several optical elements - schematically and exemplarily indicated with 34a, 34b - focused. The Coating lance 32 is rotatable and / or displaceable relative to component 30, so that a targeted coating of the component 30 in regions is possible; if necessary the focus of the laser beam 35 and / or the nozzle 38 adjustable.

Das aus der Düse 38 austretende Legierungspulver wird in Richtung des zu beschichtenden Bauteiles versprüht, wobei es zumindest teilweise durch die Hitze des Laserstrahles aufgeschmolzen wird. Der Pulverstrahl 36 wird dabei in die Nähe des Laserstrahles 35 oder durch diesen hindurch geführt. Der Pulverstrahl tritt derart aus der Düse 38 aus, dass beim Auftreffen auf die zu beschichtende Bauteiloberfläche 31a des Bauteiles 30 der erforderliche Bereich mit der gewünschten Menge Legierungspulver beaufschlagt wird. Der Fokus 35a des Laserstrahles 35 wird dabei so eingestellt, dass er genau auf der Bauteiloberfläche liegt; falls die Erhitzung hier zu stark ist, kann es auch vorteilhaft sein, die Beschichtungslanze 32 derart zu führen, dass die Bauteiloberfläche oberhalb oder unterhalb des Fokus 35a zu liegen kommt. Die Energiedichte im Brennfleck des Laserstahles beträgt dabei ca. 104 W/cm2.The alloy powder emerging from the nozzle 38 is sprayed in the direction of the component to be coated, it being at least partially melted by the heat of the laser beam. The powder jet 36 is guided in the vicinity of or through the laser beam 35. The powder jet emerges from the nozzle 38 in such a way that the required area is acted upon by the desired amount of alloy powder when it strikes the component surface 31a of the component 30 to be coated. The focus 35a of the laser beam 35 is adjusted so that it lies exactly on the component surface; if the heating is too strong here, it can also be advantageous to guide the coating lance 32 in such a way that the component surface comes to lie above or below the focus 35a. The energy density in the focal spot of the laser steel is approximately 10 4 W / cm 2 .

Es erfolgt ein kombiniertes Auf-/Einbringen des Legierungspulvers im zu beschichtenden Bereich - dem Ventilsitzbereich. Vorliegend erfolgt ein Einlegieren im 1/10 mm-Bereich verbunden mit einem Aufbringen einer einige Millimeter, ca. 2-3 mm, dicken Schicht; die mit Figur 2 gezeigte und beschriebene Verschleißschutzschicht ist auf diese Weise fest im Grundmaterial verankert.There is a combined application / introduction of the alloy powder in the coating area - the valve seat area. In the present case, alloying takes place in the 1/10 mm area combined with an application of a few millimeters, approx. 2-3 mm, thick layer; that shown and described with Figure 2 In this way, the wear protection layer is firmly anchored in the base material.

Während des Beschichtungsvorganges wird das Bauteil - der Zylinderkopf - zweckmäßigerweise gekühlt. Dabei wird ein Kompromiss zwischen einer schnellen Wärmeabfuhr zur Verhinderung eines zu weiten Aufschmelzens des Grundwerkstoffes, zwischen einem idealen Gradientenverlauf zur Ausbildung des gewünschten Gefüges und zwischen einem langsamen Abkühlen und geringen Temperaturdifferenzen zur Vermeidung von Rissen gefunden.During the coating process, the component - the cylinder head - expediently cooled. This is a compromise between a quick Heat dissipation to prevent the melting of the Base material, between an ideal gradient to form the desired structure and between a slow cooling and slight Temperature differences to avoid cracks found.

Um die Bildung unerwünschter Oxide zu vermeiden, erfolgt der gesamte Beschichtungsvorgang unter Schutzgasatmosphäre wie beispielsweise unter Argon oder Stickstoff. Der Pulverwerkstoff wird mit Schutzgas verdüst, wobei das Schutzgas in der Zuführung 37 mitgeführt oder in einer separaten Leitung zum Bereich der Düse 38 geleitet wird.To avoid the formation of unwanted oxides, the whole is done Coating process under a protective gas atmosphere such as argon or nitrogen. The powder material is sprayed with protective gas, whereby the Shielding gas carried in the feed 37 or in a separate line to the Area of the nozzle 38 is passed.

Alternativ zur beschriebenen Aufbringung des Legierungspulvers kann das Legierungspulver auch beispielsweise in Form einer Paste auf den zu beschichtenden Bereich aufgebracht werden. Die Beschichtungslanze umfasst dann lediglich die Lasereinrichtung und gegebenenfalls eine Schutzgaszuführungseinrichtung, wodurch sie baulich stark vereinfacht ist.As an alternative to applying the alloy powder as described, this can be done Alloy powder also in the form of a paste for example coating area are applied. The coating lance then includes only the laser device and possibly a protective gas supply device, which makes it structurally much simpler.

Der zu Beschichtung vorgesehene Zylinderkopfrohling wird insgesamt mit einem gewissen Aufmaß gefertigt, so dass nachfolgend eventuell bei der Beschichtung auftretender Wärmeverzug in der Endbearbeitung ausgeglichen werden kann. Die Vorbearbeitung der zu beschichtenden Ventilsitzbereiche erfolgt mit einem gewissen Untermaß, da dort eine Schicht aufgebracht wird. Während der Beschichtung des Ventilsitzbereiches 31a, 31b, 31c, 31d verfährt die Beschichtungslanze 32 mit einer Lineargeschwindigkeit von bis zu 3 m/min und wird dabei entsprechend gedreht. Es werden mehrere aneinanderliegende Raupen - je nach breite ein bis zwei - mit einem Überlappungsgrad von ca. 30-50% aufgetragen. Abschließend wird der beschichtete Bereich spanend endbearbeitet.The cylinder head blank provided for coating is combined with a a certain allowance, so that subsequently possibly in the coating occurring heat distortion in the finishing can be compensated. The The valve seat areas to be coated are pre-processed with a certain undersize, since a layer is applied there. During the Coating of the valve seat area 31a, 31b, 31c, 31d moves the Coating lance 32 with a linear speed of up to 3 m / min and will rotated accordingly. There are several adjacent caterpillars - each after width one to two - with a degree of overlap of approx. 30-50% applied. Finally, the coated area is machined.

Claims (11)

Legierungungspulver zur Beschichtung eines insbesondere aus einer Aluminium-Legierung bestehenden Bauteiles, insbesondere des Ventilsitzbereiches eines Zylinderkopfes einer Brennkraftmaschine, dadurch gekennzeichnet, dass als wesentliche Bestandteile Aluminium (Al), Silizium (Si) und Titan (Ti) enthalten sind.Alloy powder for coating a component consisting in particular of an aluminum alloy, in particular the valve seat area of a cylinder head of an internal combustion engine, characterized in that aluminum (Al), silicon (Si) and titanium (Ti) are contained as essential components. Legierungspulver nach Anspruch 1, dadurch gekennzeichnet, dass neben dem Basiselement Aluminium (Al) 10-70 gew.-%, insbesondere 20-50 gew.-% Silizium (Si) sowie 5-50 gew.-%, insbesondere 10-40 gew.-% Titan (Ti) enthalten sind.Alloy powder according to claim 1, characterized in that in addition to the base element aluminum (Al) 10-70 wt .-%, in particular 20-50 wt .-% silicon (Si) and 5-50 wt .-%, in particular 10-40 wt .-% titanium (Ti) are included. Legierungspulver nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass bis zu 25 gew.-%, insbesondere 1-15 gew.-% Nickel (Ni) und/oder bis zu 20 gew.-%, insbesondere 1-10 gew.-% Kupfer (Cu) enthalten sind.Alloy powder according to claim 1 or 2, characterized in that up to 25% by weight, in particular 1-15% by weight of nickel (Ni) and / or up to 20% by weight, in particular 1-10% by weight Copper (Cu) are included. Legierungspulver nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein Hochtemperaturschmierstoff enthalten ist.Alloy powder according to one of the preceding claims, characterized in that a high-temperature lubricant is contained. Legierungspulver nach Anspruch 4, dadurch gekennzeichnet, dass Bornitrit (BN), Graphit, B2O3 und/oder Co/Cr2O2 gewichtsanteilig mit zusammen bis zu 20 %, insbesondere mit 5-10 % enthalten sind. Alloy powder according to claim 4, characterized in that boron nitride (BN), graphite, B 2 O 3 and / or Co / Cr 2 O 2 are present in a proportion by weight of up to 20%, in particular 5-10%. Legierungspulver nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Hartstoffpartikel enthalten sind.Alloy powder according to one of the preceding claims, characterized in that hard material particles are contained. Legierungspulver nach Anspruch 6, dadurch gekennzeichnet, dass SiC und/oder B4C gewichtsanteilig mit zusammen bis zu 30 %, insbesondere 5-20 % enthalten sind.Alloy powder according to claim 6, characterized in that SiC and / or B 4 C by weight with up to 30%, in particular 5-20% are contained. Verfahren zur Beschichtung eines insbesondere aus einer Aluminium-Legierung bestehenden Bauteiles, insbesondere des Ventilsitzbereiches (31a, 31b, 31c, 31d) eines Zylinderkopfes (30) einer Brennkraftmaschine unter Verwendung eines Legierungspulvers nach einem der vorhergehenden Ansprüche mittels eines Hochenergiestrahls, insbesondere eines Laserstrahls (35), wobei das Legierungspulver (36) zumindest teilweise von der festen in die schmelzflüssige Phase umgewandelt und in einem Schmelzbad auf die Bauteiloberfläche auf-/eingebracht wird, worauf sich beim folgenden Erstarrungsprozess in der Gefügegrundmatrix eine hochschmelzende intermetallische Al-Ti Phase (20) mit eingelagerten Si-Partikeln (22) ausbildet.Process for coating an aluminum alloy in particular existing component, in particular the valve seat area (31a, 31b, 31c, 31d) of a cylinder head (30) of an internal combustion engine using an alloy powder according to any one of the preceding Claims by means of a high energy beam, in particular one Laser beam (35), wherein the alloy powder (36) at least partially from the solid is converted into the molten phase and in one Melting bath is applied to the component surface, whereupon in the subsequent solidification process in the basic matrix one high-melting intermetallic Al-Ti phase (20) with embedded Si particles (22) trains. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das Legierungspulver mittels einer geeigneten eine Düse (38) umfassenden Pulverfördereinrichtung, welche mit dem Laserstrahl (35) zusammenwirkt, auf die Bauteiloberfläche aufgebracht wird, indem das Pulver im Laserstrahl (35) oder zumindest in dessen Nähe wenigstens teilweise aufgeschmolzen wird.Method according to Claim 8, characterized in that the alloy powder is applied to the component surface by means of a suitable powder conveying device which comprises a nozzle (38) and which interacts with the laser beam (35), in that the powder is in the laser beam (35) or at least in the vicinity thereof is at least partially melted. Verfahren nach einem der Ansprüche 8 und 9, dadurch gekennzeichnet, dass das Bauteil (30) während des Beschichtens gekühlt wird.Method according to one of claims 8 and 9, characterized in that the component (30) is cooled during the coating. Verfahren nach einem der Ansprüche 8 und 9, dadurch gekennzeichnet, dass die Beschichtung unter Schutzgasatmosphäre erfolgt.Method according to one of claims 8 and 9, characterized in that the coating is carried out under a protective gas atmosphere.
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CN103302285B (en) * 2013-06-18 2015-05-20 江苏和昊激光科技有限公司 Nickel-based metal ceramic alloy powder exclusively used in laser cladding of surface of punch
CN106367752A (en) * 2013-06-28 2017-02-01 蒋红娟 Laser cladding process of copper alloy surface with liability in controlling thickness of plating
CN104018892A (en) * 2014-05-28 2014-09-03 中广核核电运营有限公司 Repairing method of valve cover sealing face pit of steam turbine high-pressure steam valve
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CN106757013A (en) * 2017-01-20 2017-05-31 青岛滨海学院 A kind of titanium alloy laser surface silicide strengthens polynary high-temperature alloy layer and preparation method thereof
CN109763125A (en) * 2019-01-18 2019-05-17 青岛滨海学院 A high-entropy alloy coating with high temperature wear resistance and its preparation process and application
WO2020254371A1 (en) * 2019-06-19 2020-12-24 Renault S.A.S Device for depositing a coating for manufacturing a valve seat
FR3097561A1 (en) * 2019-06-19 2020-12-25 Renault S.A.S Device for depositing a coating for the manufacture of a valve seat
CN110373668A (en) * 2019-07-31 2019-10-25 江西科技学院 A kind of Al alloy composite and preparation method thereof
CN112522546A (en) * 2020-10-26 2021-03-19 中北大学 Preparation of B by using SLM technology4Method for C reinforced aluminium base composite material
CN112522546B (en) * 2020-10-26 2022-02-08 中北大学 Preparation of B by using SLM technology4Method for C reinforced aluminium base composite material

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