EP0571796B1 - Surface protective coating and process for the manufacture thereof - Google Patents

Surface protective coating and process for the manufacture thereof Download PDF

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Publication number
EP0571796B1
EP0571796B1 EP93107460A EP93107460A EP0571796B1 EP 0571796 B1 EP0571796 B1 EP 0571796B1 EP 93107460 A EP93107460 A EP 93107460A EP 93107460 A EP93107460 A EP 93107460A EP 0571796 B1 EP0571796 B1 EP 0571796B1
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Prior art keywords
layer
flame spraying
spraying
produced
materials
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EP93107460A
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German (de)
French (fr)
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EP0571796A1 (en
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Peter Dipl.-Ing. Heinrich
Heinrich Prof.Dr. Kreye
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Linde GmbH
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Linde GmbH
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas

Definitions

  • the invention relates to a surface protection layer on metallic workpieces consisting of an underlayer for protection against corrosion and an upper layer for protection against wear, as well as associated manufacturing processes.
  • a main aim of the production of surface layers on metallic workpieces is to improve the mechanical wear resistance of workpieces, e.g. of waves loaded with friction.
  • the application of such wear-resistant layers is often accomplished today with very good qualities using thermal spray processes, such as autogenous flame spraying and high-speed flame spraying, arc and plasma spraying, detonation spraying and laser spraying (see Gonzbuch Strukturntechnik, Vol. 48, article “Thermal spraying - Facts and state of the art "by P. Heinrich).
  • Common materials that provide wear-resistant layers are, on the one hand, pure materials, such as molybdenum and manganese, alloy materials, such as Chromium steels and other composite or composite injection materials, such as tungsten carbides enclosed in cobalt.
  • All of these spray materials can be used as powder or in wire or rod form.
  • the respective spray material is applied in particles with a gas flow at high speed to the surface to be coated, with these particles melting or at least melting on the transport path, which is caused by the respective supply of energy - fuel gas, light or plasma arc, etc. - is effected.
  • a special variant in the production of surface layers by thermal spraying methods is that after the actual spraying process, a melting process is carried out, i.e. a second process step, which is associated with a second heating of the applied layer, which means layers with higher adhesion, tightness but with an additional one thermal stress on the respective component.
  • a surface protection layer on metallic workpieces is known, which is composed of a lower layer for protection against corrosion and an upper layer for protection against wear.
  • the lower layer consists of an electrolessly deposited nickel-phosphor layer.
  • the top layer contains hard materials, preferably titanium nitride, and is applied by means of an arc plasma process.
  • the object of the present invention is therefore to provide a surface protection layer which satisfies both high wear resistance and corrosion protection requirements.
  • An associated manufacturing process is also to be made available.
  • a surface protective layer that the lower layer directly seated on the workpiece made of a low-melting metal, selected from nickel-tin, copper-tin or lead, and the upper layer made of a material containing hard materials, preferably carbides or oxides, or of a material Dispersion layer exists.
  • top layer e.g. also so-called cermets.
  • a layer application by welding is also possible in principle (see e.g. DE-OS 40 08 091).
  • Such double layers have proven to be particularly corrosion-protecting and, at the same time, extremely wear-resistant in a large number of tests and relevant tests, for example the Kesternich test or the salt spray test.
  • the underlayer materials which are to be selected in particular according to the high level of tightness against liquids and gases, ensure the corrosion protection of the substrate material, while on the other hand the top layers to be used ensure the desired wear resistance have to worry.
  • the mechanical connection and adhesion between the two layers also meet all requirements. Further positive properties of a surface layer according to the invention consist in good adhesion also in the area of workpiece edges and in a low surface roughness.
  • a suitable method for producing such a two-layer surface protection layer is that the underlayer is produced by means of a thermal spraying process, preferably by means of high-speed flame spraying, and the top layer by means of flame spraying or preferably by means of high-speed flame spraying.
  • Another advantageous manufacturing process is characterized in that the lower layer to be initially applied to a component is applied by chemical or electrolytic deposition, while the upper layer is then again produced by means of the flame spraying process or preferably by means of the high-speed flame spraying process.
  • the underlayer can advantageously be applied by one of the thermal spray processes (flame spraying, plasma spraying, arc spraying, detonation spraying, laser spraying).
  • the two flame spraying methods namely flame spraying and high-speed flame spraying, are particularly advantageous in the calculation between cost and quality to be aimed for.
  • the corresponding spray materials e.g. a Ni-Sn alloy or a Cu-Sn alloy. It is also possible to use a composite powder, i.e. a spray material in which the metals which are to form the desired layer in the form of an alloy are contained in elementary form. A powder mixture of the components of the alloy to be formed can also be used.
  • the alloying either takes place during the spraying process itself, or it can be brought about by a suitable, subsequent heat treatment in an oven or with a flame.
  • the other options for applying an underlayer are electrolytic application or chemical deposition of appropriate materials on the respective component (chemical deposition means: material is deposited on a surface-activated component from a solution).
  • the formation of the lower layer can take place directly by the deposition of the respective alloy, or the materials forming the desired alloy are applied in two successive steps and layers and the alloy in turn is subjected to a thermal aftertreatment with a flame or in one Oven (as above!) Generated.
  • the wear-resistant upper layer is applied.
  • This is advantageously formed from chromium steel, molybdenum, manganese, oxide-ceramic materials or carbides, oxides or other materials containing hard materials, wherein in particular the cermets consisting of metal-ceramic compounds and also containing hard materials can be used.
  • the most suitable material can be selected depending on the respective application.
  • the layer is applied using the known thermal spraying method of flame spraying or preferably high-speed flame spraying.
  • the high-speed flame spraying can be classified as particularly advantageous, since this process can be used to produce layers in the desired, high-quality quality, in particular very compact and abrasion-resistant layers, with reasonable investment outlay.
  • the protective layers according to the invention are particularly suitable for components which are exposed to high requirements with regard to both corrosion and abrasion.
  • these are parts that are used in chemical plants or equipment in aggressive environments, or parts that are used in sea water.
  • the surface protection layers according to the invention have high-quality properties both with regard to wear resistance and with regard to corrosion resistance.
  • Procedural possibilities Lower layer generated by: Thermal spraying Electrolytic / chemical deposition thermal spraying of a pure material or alloy powder or wire thermal spraying of a composite powder immediate deposition of the underlayer material Deposition of several sub-materials in succession

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to surface protective coatings having particularly high wear resistance and corrosion protection properties and to processes for manufacturing same. The desired surface protective coatings are obtained according to the invention when the respective building component material is provided directly thereon with a base coat which serves as corrosion protection and on top of that with a top coat consisting of a wear-resistant material.

Description

Die Erfindung betrifft eine Oberflächenschutzschicht auf metallischen Werkstücken bestehend aus einer Unterschicht zum Schutz vor Korrosion und einer Oberschicht zum Schutz gegen Verschleiß sowie zugehörige Herstellungsverfahren.The invention relates to a surface protection layer on metallic workpieces consisting of an underlayer for protection against corrosion and an upper layer for protection against wear, as well as associated manufacturing processes.

Ein Hauptziel der Herstellung von Oberflächenschichten auf metallischen Werkstücken besteht darin, die mechanische Verschleißfestigkeit von Werkstücken, z.B. von mit Reibung beaufschlagten Wellen, zu erhöhen. Das Aufbringen solcher verschleißfester Schichten wird heute vielfach mit thermischen Spritzverfahren, wie dem autogenen Flammspritzen und Hochgeschwindigkeits-Flammspritzen, dem Lichtbogen- und Plasmaspritzen, dem Detonationsspritzen und dem Laserspritzen in sehr guten Qualitäten bewerkstelligt (siehe Jahrbuch Oberflächentechnik, Bd. 48, Artikel "Thermisches Spritzen - Fakten und Stand der Technik" von P. Heinrich). Gängige, verschleißfeste Schichten liefernde Materialien sind dabei einerseits Reinmaterialien, wie beispielsweise Molybdän und Mangan, Legierungsmaterialien, wie z.B. Chromstähle und weitere aus mehreren Materialien zusammengesetzte oder Verbundspritzmaterialien, wie beispielsweise in Cobalt eingeschlossene Wolframcarbide.A main aim of the production of surface layers on metallic workpieces is to improve the mechanical wear resistance of workpieces, e.g. of waves loaded with friction. The application of such wear-resistant layers is often accomplished today with very good qualities using thermal spray processes, such as autogenous flame spraying and high-speed flame spraying, arc and plasma spraying, detonation spraying and laser spraying (see Jahrbuch Oberflächentechnik, Vol. 48, article "Thermal spraying - Facts and state of the art "by P. Heinrich). Common materials that provide wear-resistant layers are, on the one hand, pure materials, such as molybdenum and manganese, alloy materials, such as Chromium steels and other composite or composite injection materials, such as tungsten carbides enclosed in cobalt.

Alle diese Spritzmaterialien können als Pulver oder draht- oder stabförmig zur Anwendung kommen. Beim Auftragvorgang selbst wird der jeweilige Spritzwerkstoff partikelweise mit einem Gasstrom mit hoher Geschwindigkeit auf die zu beschichtende Oberfläche aufgebracht, wobei ein Aufschmelzen oder zumindest ein Anschmelzen dieser Partikel auf dem Transportweg erfolgt, welches durch die jeweilige Energiezufuhr - Brenngas, Licht- oder Plasmalichtbogen, etc. - bewirkt wird.All of these spray materials can be used as powder or in wire or rod form. During the application process itself, the respective spray material is applied in particles with a gas flow at high speed to the surface to be coated, with these particles melting or at least melting on the transport path, which is caused by the respective supply of energy - fuel gas, light or plasma arc, etc. - is effected.

Eine spezielle Variante beim Erzeugen von Oberflächenschichten durch thermische Spritzmethoden besteht darin, daß nach dem eigentlichen Aufspritzvorgang ein Einschmelzvorgang nachgeschaltet ist, also ein zweiter Verfahrensschritt, der mit einer zweiten Erwärmung der aufgebrachten Schicht verbunden ist, wodurch Schichten mit höherer Haftfähigkeit, Dichtigkeit aber mit einer zusätzlichen thermischen Belastung des jeweiligen Bauteils entstehen.A special variant in the production of surface layers by thermal spraying methods is that after the actual spraying process, a melting process is carried out, i.e. a second process step, which is associated with a second heating of the applied layer, which means layers with higher adhesion, tightness but with an additional one thermal stress on the respective component.

In Zusammenhang mit den nun geschilderten Auftragsverfahren und den erzeugbaren, verschleißfesten Oberflächenschichten bestehen jedoch Defizite, wenn neben Eigenschaft "Verschleißfestigkeit" eine weitere Anforderung, nämlich die Korrosionsschutzfähigkeit, verlangt wird. Bei bekannten Verschleißschutzschichten besteht nämlich der Nachteil, daß diese Schichten wegen ihres porösen Aufbaus nicht gas- und flüssigkeitsdicht sind und folglich deren Untergrund nicht vor Korrosion geschützt ist.However, there are deficits in connection with the application methods now described and the wear-resistant surface layers that can be produced if, in addition to the "wear resistance" property, a further requirement, namely the ability to protect against corrosion, is required. Known wear protection layers have the disadvantage that, because of their porous structure, these layers are not gas- and liquid-tight and consequently their subsurface is not protected against corrosion.

Aus der DE 38 29 007 A1 ist eine Oberflächenschutzschicht auf metallischen Werkstücken bekannt, die sich aus einer Unterschicht zum Schutz vor Korrosion und einer Oberschicht zum Schutz gegen Verschleiß zusammensetzt. Die Unterschicht besteht aus einer stromlos abgeschiedenen Nickel-Phosphor-Schicht. Die Oberschicht enthält Hartstoffe, bevorzugt Titannitrid, und wird mittels eines Lichtbogenplasmaverfahrens aufgebracht.From DE 38 29 007 A1, a surface protection layer on metallic workpieces is known, which is composed of a lower layer for protection against corrosion and an upper layer for protection against wear. The lower layer consists of an electrolessly deposited nickel-phosphor layer. The top layer contains hard materials, preferably titanium nitride, and is applied by means of an arc plasma process.

Die Aufgabenstellung vorliegender Erfindung besteht daher darin, eine Oberflächenschutzschicht anzugeben, die sowohl hohen Anforderungen an Verschleißfestigkeit als auch an Korrosionsschutz genügt. Ebenso soll ein zugehöriges Herstellungsverfahren zur Verfügung gestellt werden.The object of the present invention is therefore to provide a surface protection layer which satisfies both high wear resistance and corrosion protection requirements. An associated manufacturing process is also to be made available.

Diese Aufgabe wird durch eine Oberflächenschutzschicht gelöst, daß die auf dem Werkstück unmittelbar aufsitzende Unterschicht aus einem niedrigschmelzenden Metall, ausgewählt aus Nickel-Zinn, Kupfer-Zinn oder Blei, und die Oberschicht aus einem Hartstoffe, bevorzugt Carbide oder Oxide, enthaltenden Material oder aus einer Dispersionsschicht besteht.This object is achieved by a surface protective layer that the lower layer directly seated on the workpiece made of a low-melting metal, selected from nickel-tin, copper-tin or lead, and the upper layer made of a material containing hard materials, preferably carbides or oxides, or of a material Dispersion layer exists.

Für die Oberschicht eignen sich besonders die mit thermischen Spritzverfahren vorteilhaft auftragbaren Materialien wie Chromstahl, Molybdän, Mangan, oxidkeramische Materialien oder Carbide, Oxide oder andere Hartstoffe enthaltende Materialien, (z.B. auch sogenannte Cermets). Ein Schichtauftrag im Wege des Schweißens ist prinzipiell ebenso möglich (siehe z.B. DE-OS 40 08 091).Materials that can be advantageously applied using thermal spraying methods, such as chrome steel, molybdenum, manganese, oxide-ceramic materials or carbides, oxides or other hard materials, are particularly suitable for the top layer (e.g. also so-called cermets). A layer application by welding is also possible in principle (see e.g. DE-OS 40 08 091).

Derartige Doppelschichten haben sich in einer Vielzahl von Versuchen und einschlägigen Prüfungen, z.B. dem Kesternich-Test oder dem Salzsprühtest, als besonders korrosionsschützend und gleichzeitig ausgezeichnet verschleißfest erwiesen. Die insbesondere nach hoher Dichtigkeit gegen Flüssigkeiten und Gasen auszuwählenden Unterschichtsmaterialien sorgen hierbei für den Korrosionsschutz des Substratmaterials, während andererseits die anzuwendenden Oberschichten für die gewünschte Verschleißfestigkeit zu sorgen haben. Bei den erfindungsgemäßen Schichten wird darüber hinaus auch die mechanische Verbindung und Haftung zwischen den beiden Schichten allen Anforderungen gerecht. Weitere positive Eigenschaften einer erfindungsgemäßen Oberflächenschicht bestehen in einer guten Haftung auch im Bereich von Werkstückkanten sowie in einer geringen Oberflächenrauhigkeit.Such double layers have proven to be particularly corrosion-protecting and, at the same time, extremely wear-resistant in a large number of tests and relevant tests, for example the Kesternich test or the salt spray test. The underlayer materials, which are to be selected in particular according to the high level of tightness against liquids and gases, ensure the corrosion protection of the substrate material, while on the other hand the top layers to be used ensure the desired wear resistance have to worry. In the layers according to the invention, the mechanical connection and adhesion between the two layers also meet all requirements. Further positive properties of a surface layer according to the invention consist in good adhesion also in the area of workpiece edges and in a low surface roughness.

Ein geeignetes Verfahren zur Herstellung einer solchen zweilagigen Oberflächenschutzschicht besteht darin, daß die Unterschicht mittels eines thermischen Spritzverfahrens, vorzugsweise mittels Hochgeschwindigkeits-Flammspritzens, und die Oberschicht mittels Flammspritzens oder bevorzugt mittels Hochgeschwindigkeits-Flammspritzens erzeugt wird.A suitable method for producing such a two-layer surface protection layer is that the underlayer is produced by means of a thermal spraying process, preferably by means of high-speed flame spraying, and the top layer by means of flame spraying or preferably by means of high-speed flame spraying.

Ein weiteres vorteilhaftes Herstellungsverfahren ist dadurch gekennzeichnet, daß die auf ein Bauteil zunächst aufzubringende Unterschicht durch chemisches oder elektrolytisches Abscheiden aufgebracht wird, während die Oberschicht anschließend wiederum mittels Flammspritzverfahrens oder bevorzugt mittels des Hochgeschwindigkeits-Flammspritzenverfahrens, erzeugt wird.Another advantageous manufacturing process is characterized in that the lower layer to be initially applied to a component is applied by chemical or electrolytic deposition, while the upper layer is then again produced by means of the flame spraying process or preferably by means of the high-speed flame spraying process.

Die Erzeugung von erfindungsgemäßen Oberflächenschichten wird im folgenden beispielhaft näher erläutert (siehe hierzu auch anhängende Tabelle).The generation of surface layers according to the invention is explained in more detail below as an example (see also the attached table).

Das Aufbringen der Unterschicht kann in einer ersten Variante mit Vorteil durch eines der thermischen Spritzverfahren (Flammspritzen, Plasmaspritzen, Lichtbogenspritzen, Detonationsspritzen, Laserspritzen) erfolgen. Hierbei sind die beiden Flammspritzmethoden, nämlich das Flammspritzen und das Hochgeschwindigkeits-Flammspritzen, im Kalkül zwischen Kostenaufwand und anzustrebender Qualität, besonders vorteilhaft. Dabei gelangen - entsprechend den auszubildenden Schichten - die entsprechenden Spritzmaterialien, also z.B. eine Ni-Sn-Legierung oder eine Cu-Sn-Legierung, zur Anwendung. Es ist auch möglich, ein Verbundpulver anzuwenden, d.h. ein Spritzmaterial, in dem die Metalle, die die gewünschte Schicht in Form einer Legierung bilden sollen, elementar enthalten sind. Ebenso ist auch ein Pulvergemisch aus den Komponenten der zu bildenden Legierung anwendbar.In a first variant, the underlayer can advantageously be applied by one of the thermal spray processes (flame spraying, plasma spraying, arc spraying, detonation spraying, laser spraying). Here, the two flame spraying methods, namely flame spraying and high-speed flame spraying, are particularly advantageous in the calculation between cost and quality to be aimed for. The corresponding spray materials, e.g. a Ni-Sn alloy or a Cu-Sn alloy. It is also possible to use a composite powder, i.e. a spray material in which the metals which are to form the desired layer in the form of an alloy are contained in elementary form. A powder mixture of the components of the alloy to be formed can also be used.

Bei den Verbundpulvern und den Pulvergemischen erfolgt die Legierungsbildung entweder beim Spritzvorgang selbst, oder sie kann durch eine geeignete, nachfolgende Wärmebehandlung in einem Ofen oder mit einer Flamme bewirkt werden.In the case of the composite powders and the powder mixtures, the alloying either takes place during the spraying process itself, or it can be brought about by a suitable, subsequent heat treatment in an oven or with a flame.

Die weiteren Möglichkeiten zum Aufbringen einer Unterschicht bestehen im elektrolytischen Aufbringen oder chemischen Abscheiden von entsprechenden Materialien auf das jeweilige Bauteil (chemisches Abscheiden heißt: auf ein oberflächenaktiviertes Bauteil wird aus einer Lösung Material niedergeschlagen).The other options for applying an underlayer are electrolytic application or chemical deposition of appropriate materials on the respective component (chemical deposition means: material is deposited on a surface-activated component from a solution).

Dabei kann die Bildung der Unterschicht im Falle von Legierungsmaterialien unmittelbar durch die Abscheidung der jeweiligen Legierung erfolgen, oder es werden die die gewünschte Legierung bildenden Materialien in zwei aufeinanderfolgenden Schritten und Schichten nacheinander aufgebracht und die Legierung wiederum durch eine thermische Nachbehandlung mit einer Flamme oder in einem Ofen (wie oben!) erzeugt.In the case of alloy materials, the formation of the lower layer can take place directly by the deposition of the respective alloy, or the materials forming the desired alloy are applied in two successive steps and layers and the alloy in turn is subjected to a thermal aftertreatment with a flame or in one Oven (as above!) Generated.

Nach dem Aufbringen der Unterschicht nach einer der beschriebenen Methoden erfolgt das Auftragen der verschleißfesten Oberschicht. Diese wird mit Vorteil aus Chromstahl, Molybdän, Mangan, oxidkeramischen Materialien oder Carbide, Oxide oder andere Hartstoffe enthaltende Materialien gebildet, wobei insbesondere auch die aus Metall-Keramik-Verbindungen bestehenden, ebenfalls Hartstoffe enthaltenden Cermets anwendbar sind. Das jeweils am besten geeignete Material kann dabei abhängig vom jeweiligen Anwendungsfall ausgewählt werden. Der Schichtauftrag erfolgt mit dem bekannten thermischen Spritzverfahren des Flammspritzens oder bevorzugt des Hochgeschwindigkeits-Flammspritzens. Das Hochgeschwindigkeits-Flammspritzen ist als besonders vorteilhaft einzustufen, da mit diesem Verfahren mit vertretbarem Investitionsaufwand Schichten in gewünschter, hochwertiger Qualität, nämlich insbesondere sehr kompakte und abriebfeste Schichten, herstellbar sind.After applying the lower layer using one of the methods described, the wear-resistant upper layer is applied. This is advantageously formed from chromium steel, molybdenum, manganese, oxide-ceramic materials or carbides, oxides or other materials containing hard materials, wherein in particular the cermets consisting of metal-ceramic compounds and also containing hard materials can be used. The most suitable material can be selected depending on the respective application. The layer is applied using the known thermal spraying method of flame spraying or preferably high-speed flame spraying. The high-speed flame spraying can be classified as particularly advantageous, since this process can be used to produce layers in the desired, high-quality quality, in particular very compact and abrasion-resistant layers, with reasonable investment outlay.

Weitere geeignete Verschleißschichten sind sogenannte Dispersionsschichten, bei denen die Hartstoffe in eine, aus dem korrosionsbeständigen Unterschichtmaterial bestehende Matrix eingebettet sind. Derartige Schichten lassen sich wiederum durch thermisches Spritzen erzeugen, wobei

  • ein Pulvergemisch oder ein agglomeriertes Pulver verwendet wird, dessen Komponenten aus Hartstoff oder Hartlegierung und korrosionsbeständigem Material bestehen, oder
  • ein ummanteltes Pulver verwendet wird, bei dem die einzelnen Partikel des Hartstoffs oder der Hartlegierung elektrolytisch mit korrosionsbeständigem Material beschichtet sind.
Further suitable wear layers are so-called dispersion layers, in which the hard materials are embedded in a matrix consisting of the corrosion-resistant underlayer material. Such layers can in turn be produced by thermal spraying, wherein
  • a powder mixture or an agglomerated powder is used, the components of which consist of hard material or hard alloy and corrosion-resistant material, or
  • a coated powder is used in which the individual particles of the hard material or hard alloy are electrolytically coated with corrosion-resistant material.

Die verschiedenen Möglichkeiten, eine erfindungsgemäße Doppelschicht herzustellen, sind in der nachfolgenden Tabelle nochmals gezeigt. Bei der Durchführung der einzelnen Auftragsschritte mit den verschiedenen Methoden wird die jeweilige Methode in der jeweils üblichen Weise mit Abstimmung auf das aufzutragende Material angewendet. Es sind also keine besonderen Verfahrensabwandlungen notwendig, um die erfindungsgemäßen Ober- oder Unterschichten zu erzeugen.The various options for producing a double layer according to the invention are shown again in the table below. When carrying out the individual Order steps with the different methods, the respective method is applied in the usual way with coordination to the material to be applied. No special process modifications are therefore necessary in order to produce the upper or lower layers according to the invention.

Die erfindungsgemäßen Schutzschichten eignen sich vor allem für Bauteile, die hohen Anforderungen sowohl hinsichtlich Korrosion als auch hinsichtlich Abrieb ausgesetzt sind. Beispielsweise sind dies Teile, die in chemischen Anlagen oder Apparaturen in aggressiver Umgebungen zur Anwendung kommen, oder auch Teile, die in Meerwasser eingesetzt werden. Die erfindungsgemäßen Oberflächenschutzschichten besitzen jedenfalls sowohl hinsichtlich Verschleißfestigkeit als auch hinsichtlich Korrosionswiderstand hochwertige Eigenschaften. Verfahrensmöglichkeiten Unterschicht erzeugt durch: Thermisches Spritzen Elektrolytisches / chemisches Abscheiden thermisches Aufspritzen eines Reinmaterial- oder Legierungspulvers, -drahtes thermisches Aufspritzen eines Verbundpulvers unmittelbare Abscheidung des Unterschichtmaterials Abscheidung von mehreren Untermaterialien nacheinander Oberschicht erzeugt durch: Thermisches Aufspritzen Thermisches Aufspritzen Flammspritzen, vorzugsweise jedoch Hochgeschwindigkeits-Flammspritzen Flammspritzen, vorzugsweise jedoch Hochgeschwindigkeits-Flammspritzen The protective layers according to the invention are particularly suitable for components which are exposed to high requirements with regard to both corrosion and abrasion. For example, these are parts that are used in chemical plants or equipment in aggressive environments, or parts that are used in sea water. In any case, the surface protection layers according to the invention have high-quality properties both with regard to wear resistance and with regard to corrosion resistance. Procedural possibilities Lower layer generated by: Thermal spraying Electrolytic / chemical deposition thermal spraying of a pure material or alloy powder or wire thermal spraying of a composite powder immediate deposition of the underlayer material Deposition of several sub-materials in succession Upper class generated by: Thermal spraying Thermal spraying Flame spraying, but preferably high speed flame spraying Flame spraying, but preferably high speed flame spraying

Claims (4)

  1. Surface-protective layer on metal workpieces consisting of a base layer for protection against corrosion and a top layer for protection against wear, characterized in that the base layer, which rests directly on the workpiece, consists of a low-melting metal selected from the group consisting of nickel-tin, copper-tin or lead and the top layer consists of a material containing hard materials, preferably carbides or oxides, or of a dispersion layer.
  2. Surface-protective layer according to Claim 1, characterized in that the top layer consists of chromium steel, molybdenum, manganese or oxide-ceramic materials.
  3. Process for producing a surface-protective layer according to Claim 1 or 2, characterized in that the base layer is produced by means of a thermal spraying process, preferably by means of high-speed flame spraying, and the top layer is produced by means of flame spraying or preferably by means of high-speed flame spraying.
  4. Process for producing the surface-protective layer according to Claim 1 or 2, characterized in that the base layer is produced by means of chemical or electrolytic deposition and the top layer is produced by means of flame spraying or preferably by means of high-speed flame spraying.
EP93107460A 1992-05-27 1993-05-07 Surface protective coating and process for the manufacture thereof Expired - Lifetime EP0571796B1 (en)

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DE4217612A DE4217612A1 (en) 1992-05-27 1992-05-27 Surface protective layer and method for producing the same
DE4217612 1992-05-27

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DE4336664A1 (en) * 1993-10-27 1995-05-04 Demetron Gmbh Workpieces made of non-corrosion-resistant metals with coatings applied using the PVD process
FR2708940B1 (en) * 1993-08-12 1995-09-22 Snecma Method of hardening metal parts.
US5931269A (en) * 1997-04-21 1999-08-03 Alliedsignal Inc. Aircraft wheel part with corrosion and wear resistance
GB9807020D0 (en) 1998-04-02 1998-06-03 Bamford Excavators Ltd A method of marking a mechanical element, an encoding scheme, a reading means for said marking and an apparatus for determining the position of said element
RU2530975C1 (en) * 2013-05-16 2014-10-20 Фонд поддержки научной, научно-технической и инновационной деятельности "Энергия без границ" (Фонд "Энергия без границ") Coating for application on driving elements of stop and control valves
CN106756745B (en) * 2017-02-07 2019-01-25 和县隆盛精密机械有限公司 A kind of heat resistant and wear resistant damage polishing mechanical arm coating

Citations (1)

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Publication number Priority date Publication date Assignee Title
DE3604762A1 (en) * 1985-06-22 1987-01-02 Winfried Heinzel METHOD FOR COATING HOUSEHOLD OBJECTS WITH AN NON-STICKING LAYER AND HOUSEHOLD OBJECT

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JPS63118058A (en) * 1986-11-05 1988-05-23 Toyota Motor Corp Member thermally sprayed with ceramic and its production
DE3829007A1 (en) * 1988-08-26 1990-03-01 Multi Arc Gmbh METHOD FOR PLASMA COATING OBJECTS WITH A HARD MATERIAL

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
DE3604762A1 (en) * 1985-06-22 1987-01-02 Winfried Heinzel METHOD FOR COATING HOUSEHOLD OBJECTS WITH AN NON-STICKING LAYER AND HOUSEHOLD OBJECT

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EP0571796A1 (en) 1993-12-01
DE4217612A1 (en) 1993-12-02
ES2092176T3 (en) 1996-11-16
ATE143064T1 (en) 1996-10-15
DE59303820D1 (en) 1996-10-24

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