EP0167793A1 - Method and coating material for producing ceramic metal bond coats - Google Patents

Method and coating material for producing ceramic metal bond coats Download PDF

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Publication number
EP0167793A1
EP0167793A1 EP85106773A EP85106773A EP0167793A1 EP 0167793 A1 EP0167793 A1 EP 0167793A1 EP 85106773 A EP85106773 A EP 85106773A EP 85106773 A EP85106773 A EP 85106773A EP 0167793 A1 EP0167793 A1 EP 0167793A1
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European Patent Office
Prior art keywords
metal
ceramic
coating material
spraying
metal bond
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EP85106773A
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German (de)
French (fr)
Inventor
Welf Dr. Amende
Paul Dr. Harmathy
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MAN AG
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MAN Maschinenfabrik Augsburg Nuernberg AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material

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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)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

For producing relatively thick ceramic insulating layers, a coating method is described, in which ceramic and metal are applied as a composite material to a substrate by a spraying method. The precipitation material is fed in the form of a ceramic tube with a metal core to the spraying device. During the spraying step, the ceramic tube also acts as an insulation for the metal core in order to avoid overheating or vaporisation of the metal. <IMAGE>

Description

Die Erfindung bezieht sich auf ein Verfahren zum Herstellen von Keramik/Metall-Verbundschichten im Spritzverfahren sowie auf ein Beschichtungsmaterial dazu.The invention relates to a method for producing ceramic / metal composite layers by spraying and to a coating material therefor.

Es ist bekannt, hohen Temperaturen ausgesetzte Gegenstände mit einer Keramikbeschichtung zu isolieren. Die Schichtdicke des Keramiküberzuges richtet sich nach den Isolieranforderungen, wobei jedoch aufgrund der hohen Temperaturspannungen, die im Keramikmaterial auftreten können die Schichtdicke eines Keramiküberzuges stark begrenzt ist. Es sind allerdings reine Keramikschichten mit stärkerer Schichtdicke mit dem Plasmaspritzverfahren herstellbar. Das auf ein Subsatrat aufgebrachte Material hat bei diesem Verfahren sehr hohe Temperaturen und einen geringen Temperaturgradienten, so daß etwaige Spannungen in den noch flüssigen Gebieten abgebaut werden können. Jedoch sind diese Schichten bei insbesondere stärkerem Temperaturwechsel nicht beständig.It is known to insulate objects exposed to high temperatures with a ceramic coating. The layer thickness of the ceramic coating depends on the insulation requirements, but due to the high temperature stresses that can occur in the ceramic material, the layer thickness of a ceramic coating is very limited. However, pure ceramic layers with a thicker layer thickness can be produced using the plasma spraying process. The material applied to a substrate has very high temperatures and a low temperature gradient in this process, so that any tensions in the still liquid areas can be reduced. However, these layers are not stable in the event of particularly strong temperature changes.

Die Schichtdickengrenze läßt sich bekannterweise mit einer Verbundbeschichtung aus Keramik und Metall erweitern. Zur Herstellung einer solchen Verbundschicht wird zunächst eine Keramikschicht und darauf eine Metallschicht aufgebracht. Dieses bekannte Verfahren erfordert jedoch zwei Arbeitsgänge.As is known, the layer thickness limit can be extended with a composite coating of ceramic and metal. To produce such a composite layer, a ceramic layer is first applied and then a metal layer. However, this known method requires two operations.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art zu schaffen, mit dem sich eine beständige Keramik/Metall-Schicht mit möglichst geringem Arbeitsaufwand auf ein Substrat aufbringen läßt.The invention has for its object to provide a method of the type mentioned, with which a durable ceramic / metal layer can be applied to a substrate with as little work as possible.

Die Aufgabe ist erfindungsgemäß mit den im Anspruch 1 gekennzeichneten Merkmalen gelöst.The object is achieved with the features characterized in claim 1.

Mit dem erfindungsgemäßen Verfahren wird ein einziger Arbeitsgang, nämlich das Aufspritzen der Materialmischung benötigt, wobei das Keramikmaterial bei einer geringeren Temperatur als bei den bekannten Verfahren verarbeitet werden kann, nachdem es auf dem Substrat in das weichere Metall eingebettet wird. Bei der so erzeugten Isolierschicht sind die beiden Komponenten, nämlich das Metall und das Keramikmaterial innerhalb der gesamten Schicht vermischt, so daß außerdem eine bessere Aufnahme von Spannungskräften durch das Metall erfolgen kann, als es bei der Nacheinanderbeschichtung von Keramik und Metall möglich ist. Es hat sich auch gezeigt, daß eine derartige Schicht eine hohe physikalische, mechanische und chemische Beständigkeit hat. Sie eignet sich somit nicht nur zur Herstellung von Wärmeisolierschichten, sondern auch für verschleißhemmende Oberzüge.With the method according to the invention, a single operation, namely the spraying of the material mixture, is required, the ceramic material being able to be processed at a lower temperature than in the known methods after it has been embedded in the softer metal on the substrate. In the insulating layer produced in this way, the two components, namely the metal and the ceramic material, are mixed within the entire layer, so that, in addition, a better absorption of tensile forces by the metal can take place than is possible with the successive coating of ceramic and metal. It has also been shown that such a layer has a high physical, mechanical and chemical resistance. It is therefore not only suitable for the production of thermal insulation layers, but also for wear-resistant top layers.

Gemäß einer weiteren Ausgestaltung der Erfindung wird das Metall in im Keramikmaterial eingebetteter Form dem Aufspritzvorgang zugeführt.According to a further embodiment of the invention, the metal is fed to the spraying process in the form embedded in the ceramic material.

Dies hat den Vorteil, daß die hohen, zur Aufschmelzung des Keramikmaterials erforderlichen Temperaturen nicht direkt das Metall beaufschlagen und somit eine Verdampfung des Metalls im Aufspritzvorgang vermieden wird.This has the advantage that the high temperatures required for the melting of the ceramic material do not directly affect the metal and thus evaporation of the metal in the spraying process is avoided.

Vorzugsweise wird eine Aufbereitung des Beschichtungsmaterials in der Form eines Keramikrohres mit einer Metall- oder metallhaltigen Seele vorgeschlagen.Preparation of the coating material in the form of a ceramic tube with a metal or metal-containing core is preferably proposed.

Dieses Verbund-Beschichtungsmaterial wird in einer einfachen Form durch Ziehen von Keramikrohren und Auffüllen mit dem entsprechenden Metall hergestellt. Das Metall oder ein metallhaltiges Material kann dabei als Pulver, in flüssiger Form oder als Draht in das Keramikrohr eingebracht werden.This composite coating material is made in a simple form by drawing ceramic pipes and filling them with the appropriate metal. The metal or a metal-containing material can be introduced into the ceramic tube as powder, in liquid form or as wire.

Ein so aufbereitetes Beschichtungsmaterial hat viele Vorteile. Bei der Verwendung eines Drahtkernes kann eine Endlosschlaufe durch Aufreihen von Keramikrohrstücken hergestellt werden. Der Draht und das Keramikrohr können - wenn erforderlich oder für einen bestimmten Anwendungsfall zweckmäßig - mit unterschiedlichen Vorschubgeschubsgeschwindigkeiten angetrieben werden.A coating material prepared in this way has many advantages. When using a wire core, an endless loop can be made by lining up ceramic tube pieces. The wire and the ceramic tube can - if necessary or appropriate for a specific application - be driven at different feed speeds.

Es ist ferner möglich, die Konzentration des Kernmaterials kontinuierlich zu variieren. Dieses kann gegebenenfalls auch elektronisch während des Aufspritzvorganges erfolgen, indem ein pulverfömiges Kernmaterial elektronisch in Abhängigkeit des momentanen Beschichtungszustandes gemischt und in das Keramikrohr eingeführt wird.It is also possible to vary the concentration of the core material continuously. This can optionally also be done electronically during the spraying process by electronically mixing a powdery core material depending on the current coating condition and introducing it into the ceramic tube.

Um eine gute Haftung der Schicht auf dem Substrat zu erreichen, ist es je nach Beschaffenheit des Substrats zweckmäßig, zunächst eine metallreiche Schicht aufzubringen und kontinuierlich die Keramikkonzentration mit zunehmender Schichtdicke zu erhöhen, um die gewünschte Isolier- und verschleißhemmende Wirkung zu erreichen. Die Konzentration in der Beschichtung wird durch Ändern der Konzentration eines aus Metall und Keramikmaterial bestehenden Kernmaterials oder durch Veränderung des Relativvorschubes zwischen Kernmaterial und Keramikrohr erreicht.In order to achieve good adhesion of the layer to the substrate, it is advisable, depending on the nature of the substrate, to first apply a metal-rich layer and to continuously increase the ceramic concentration with increasing layer thickness in order to achieve the desired insulation and wear-resistant effect. The concentration in the coating is achieved by changing the concentration of a core material consisting of metal and ceramic material or by changing the relative feed between core material and ceramic tube.

Im Aufspritzvorgang dient das Keramikrohr gleichzeitig zur Wärmeisolierung für das Metall, so daß dieses nicht bis auf die Verdampfungstemperatur erhitzt wird. Es konnte festgestellt werden, daß das Material im Spritzvorgang in ähnlicher Form eines gespitzten Bleistiftes vom Stab abgetragen wird, wobei Keramik und Metall gleichzeitig auf das Substrat aufgebracht werden.In the spraying process, the ceramic tube also serves as heat insulation for the metal, so that it is not heated up to the evaporation temperature. It was found that the material is removed from the rod in a similar form to a sharpened pencil, with ceramic and metal being applied to the substrate at the same time.

In der Zeichnung ist ein Ausführungsbeispiel schematisch dargestellt. Das Beschichtungsmaterial ist ein Stab 12, bestehend aus einem Keramikrohr 10, z.B. aus Aluminiumoxid, Zirconoxid mit einer Metallseele 11, z.B. aus Co, CrNi, Metall/Keramikmaterial, der in einer Spritzvorrichtung 13 aufgeschmolzen wird. Mit Hilfe eines gasförmigen Strömungsmittels 14 wird das aufgeschmolzene Verbundmaterial auf ein Substrat 15 aufgebracht.In the drawing, an embodiment is shown schematically. The coating material is a rod 12 consisting of a ceramic tube 10, e.g. made of aluminum oxide, zirconium oxide with a metal core 11, e.g. made of Co, CrNi, metal / ceramic material, which is melted in a spraying device 13. With the help of a gaseous fluid 14, the melted composite material is applied to a substrate 15.

Der Stab 12 wird innerhalb der Spritzvorrichtung 13 auf eine Temperatur erwärmt, die das Keramikmaterial 10 zum Schmelzen bringt. Isoliert durch das Keramikrohr 10 erhitzt sich der Metallkern 11 nicht bis auf die von außen beaufschlagte Temperatur, sondern auf eine niedrigere Temperatur, die ausreicht um das Metall zum Schmelzen, jedoch nicht zum Verdampfen zu bringen. Der Abtrag des Beschichtungsmaterials erfolgt an der Spitze 16 des Stabes mit konischem Verlauf, so daß mit dem Abtrag des Keramikmaterials von der Spitze aus flüssiges Metall mitgezogen werden kann.The rod 12 is heated within the spray device 13 to a temperature which causes the ceramic material 10 to melt. Insulated by the ceramic tube 10, the metal core 11 does not heat up to the externally applied temperature, but to a lower temperature which is sufficient around the metal to melt, but not to evaporate. The removal of the coating material takes place at the tip 16 of the rod with a conical shape, so that when the ceramic material is removed from the tip, liquid metal can be drawn along.

Claims (3)

1. Verfahren zur Herstellung von Keramik/Metall-Verbundbeschichtungen im Spritzverfahren, dadurch gekennzeichnet, daß das Metall zusammen mit dem Keramikmaterial aufgespritzt wird.1. A process for the production of ceramic / metal composite coatings by spraying, characterized in that the metal is sprayed on together with the ceramic material. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Metall in im Keramikmaterial eingebetteter Form dem Aufspritzvorgang zugeführt wird.2. The method according to claim 1, characterized in that the metal is fed to the spraying process in the form embedded in the ceramic material. 3. Beschichtungsmaterial zum Durchführen des Verfahrens gemäß Anspruch 1, dadurch gekennzeichnet, daß das Beschichtungsmaterial die Form eines Keramikrohres (10) mit einer Metallseele (11) oder einer metallhaltigen Seele hat.3. Coating material for performing the method according to claim 1, characterized in that the coating material has the shape of a ceramic tube (10) with a metal core (11) or a metal-containing core.
EP85106773A 1984-06-14 1985-06-01 Method and coating material for producing ceramic metal bond coats Withdrawn EP0167793A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3422138 1984-06-14
DE19843422138 DE3422138A1 (en) 1984-06-14 1984-06-14 METHOD AND COATING MATERIAL FOR PRODUCING CERAMIC / METAL COMPOSITE COATINGS

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EP0167793A1 true EP0167793A1 (en) 1986-01-15

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JP (1) JPS6112861A (en)
DE (1) DE3422138A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62243778A (en) * 1986-04-15 1987-10-24 Inoue Japax Res Inc Electrode for coating
DE19538046C2 (en) * 1995-10-13 1997-12-11 Forschungszentrum Juelich Gmbh Layer system
DE19625274A1 (en) * 1996-06-25 1998-01-02 Lwk Plasmakeramik Gmbh & Co Kg Mechanically reinforcing ceramic moulded parts

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998322A (en) * 1957-12-31 1961-08-29 Frank R Strate Method of hard facing metal
US3020182A (en) * 1958-09-26 1962-02-06 Gen Electric Ceramic-to-metal seal and method of making the same
FR1434948A (en) * 1964-11-18 1966-04-15 Sfec Improvement in manufacturing processes for fiber-reinforced parts and coatings
FR1467716A (en) * 1965-02-10 1967-01-27 Avco Corp Spray coating
FR1536493A (en) * 1966-07-22 1968-08-16 Montedison Spa High strength protective coatings and method thereof for their application to interior surfaces of hydrocarbon cracking reactors
GB1258262A (en) * 1968-06-10 1971-12-30
US4004042A (en) * 1975-03-07 1977-01-18 Sirius Corporation Method for applying a wear and impact resistant coating
US4248940A (en) * 1977-06-30 1981-02-03 United Technologies Corporation Thermal barrier coating for nickel and cobalt base super alloys
FR2467243A1 (en) * 1979-10-15 1981-04-17 United Technologies Corp CARBON-TYPE MCRALY-TYPE COATINGS, COATED ARTICLES AND METHODS THEREFOR

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4481237A (en) * 1981-12-14 1984-11-06 United Technologies Corporation Method of applying ceramic coatings on a metallic substrate
JPS58194782A (en) * 1982-03-05 1983-11-12 ロ−ルス−ロイス・リミテツド Composite material coating material and application to article

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998322A (en) * 1957-12-31 1961-08-29 Frank R Strate Method of hard facing metal
US3020182A (en) * 1958-09-26 1962-02-06 Gen Electric Ceramic-to-metal seal and method of making the same
FR1434948A (en) * 1964-11-18 1966-04-15 Sfec Improvement in manufacturing processes for fiber-reinforced parts and coatings
FR1467716A (en) * 1965-02-10 1967-01-27 Avco Corp Spray coating
FR1536493A (en) * 1966-07-22 1968-08-16 Montedison Spa High strength protective coatings and method thereof for their application to interior surfaces of hydrocarbon cracking reactors
GB1258262A (en) * 1968-06-10 1971-12-30
US4004042A (en) * 1975-03-07 1977-01-18 Sirius Corporation Method for applying a wear and impact resistant coating
US4248940A (en) * 1977-06-30 1981-02-03 United Technologies Corporation Thermal barrier coating for nickel and cobalt base super alloys
FR2467243A1 (en) * 1979-10-15 1981-04-17 United Technologies Corp CARBON-TYPE MCRALY-TYPE COATINGS, COATED ARTICLES AND METHODS THEREFOR

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SOVIET POWDER METALLURGY AND METAL CERAMICS, Band 11, Nr. 3, M{rz 1972, Seiten 253-254, Consultants Bureau, New York, US; D.M. KARPINOS et al.: "Improving the adhesion of plasma-sprayed coatings to articles" *

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JPS6112861A (en) 1986-01-21
DE3422138C2 (en) 1991-06-20
DE3422138A1 (en) 1985-12-19

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