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EP0401611B1 - High temperature composite material, process for its manufacture and its use - Google Patents

High temperature composite material, process for its manufacture and its use Download PDF

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Publication number
EP0401611B1
EP0401611B1 EP90109913A EP90109913A EP0401611B1 EP 0401611 B1 EP0401611 B1 EP 0401611B1 EP 90109913 A EP90109913 A EP 90109913A EP 90109913 A EP90109913 A EP 90109913A EP 0401611 B1 EP0401611 B1 EP 0401611B1
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EP
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Prior art keywords
weight
temperature composite
platinum
materials
rhodium
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EP90109913A
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German (de)
French (fr)
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EP0401611A1 (en
Inventor
Erich Prof. Dr. Lugscheider
Heinz Prof Dr. Eschnauer
Johannes Dr. Wilden
Frank Dipl.-Phys Büche
Helmut Dr. Meinhardt
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HC Starck GmbH
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HC Starck GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • 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
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
    • 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
    • C22C32/0047—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 with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—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 with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component

Definitions

  • the present invention relates to a new corrosion and wear-resistant high-temperature composite material consisting of MCrAly matrix metal, where M is Fe, Co and / or Ni and Y may be absent, with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, as well as from hard material particles embedded in the matrix metal, a process for producing this high-temperature composite material and its use.
  • MCrAlY alloys The use of materials with the general designation MCrAlY alloys is known from the field of gas turbine construction, in particular aircraft engines, where M is a metal from the group of iron, cobalt and nickel or combinations of these elements. Materials of this type are described in US-A-3 874 901, US-A-3 928 026, US-A-3 542 530 and US-A-3 754 903.
  • MCrAlY alloys with the aim of corrosion resistance has led to alloy types containing precious metals.
  • an MCrAlY alloy with 3 to 12% by weight of platinum or rhodium is described in US Pat. No. 3,918,139; platinum-containing NiCrAl-based coating alloys have proven excellent corrosion resistance in the past in many cases.
  • hard materials such as oxides and nitrides can be added to the base alloys in accordance with US Pat. Nos. 3,879,831 and 4,124,737.
  • US Pat. No. 4,275,124 known to increase the wear behavior of MCrAlY alloys by carbides formed in situ or by alloyed carbides.
  • the carbides embedded in the MCrAlY matrix react more or less strongly in the matrix due to the physical and chemical properties of this composite system under the operating temperatures that occur.
  • the reaction rate increases with increasing temperature zu and carbides of the 6th subgroup (eg Cr3C2) are degraded faster at the same temperature than that of the 4th subgroup (e.g. TiC, NbC). Since the efficiency of many systems operating at high temperatures can be further increased by increasing the temperature, high-temperature stable, corrosion and wear-resistant materials are required.
  • the object of the invention is therefore to improve the high-temperature stability of the composite materials made of MCrAlY matrix and hard materials in order to overcome the disadvantages of the known material combinations. Accordingly, temperature-stable, corrosion-resistant and wear-resistant alloys should be made available, which can be used at temperatures of 600 to 1100 ° C.
  • MCrAl (Y) material (with or without yttrium content) which, in addition to platinum or rhodium carbides, is the 4th and / or 5th and / or 6th subgroup of the periodic table Contains items. It has been shown that these additional alloy elements greatly reduce the degradation reactions of the carbides with the matrix, so that carbide particles embedded in the matrix maintain their wear-inhibiting effect for longer. Mixed carbides can also be used.
  • the additional positive effect of platinum in this context is known to be an improvement in the corrosion behavior through improved oxide adhesion on the surface.
  • the platinum content of the MCrAlY matrix can be up to 15% by weight, the carbide content between 0.01 and 75% by weight. % vary.
  • This invention thus relates to a corrosion and wear-resistant high-temperature composite material consisting of MCrAlY matrix metal, where M is Fe, Co and / or Ni and Y may be absent, with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, as well as from hard material particles embedded in the matrix metal in the form of carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof in quantities of 0.01 to 75% by weight, preferably 5 to 75% by weight, based on the high-temperature composite material.
  • the carbide particle size is less than 50 ⁇ m.
  • the carbide particles contained are compact.
  • Corresponding matrix alloys of the MCrAlY type with platinum and / or rhodium additives in powder form as matrix materials for composite materials with dispersed hard material powders have hitherto not been disclosed.
  • the MCrAlY hard alloys according to the invention can preferably by suspension spraying, mechanical alloying or mixing of composite powders of MCrAlY, platinum and / or rhodium and hard materials in the form of carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof, which are produced 5 to 15% by weight of platinum and / or rhodium and 0.01 to 75% by weight, preferably 5 to 75% by weight, containing metal carbide can be obtained.
  • the invention also relates to the use of the high-temperature composite materials for the production of surface protective layers.
  • the powders are processed to form the surface protective layers, preferably by build-up welding or thermal spraying processes such as plasma spraying, powder plasma build-up welding, high-speed flame spraying or laser coating.
  • This invention also relates to the use of the high-temperature composite materials according to the invention for the production of compact components which are obtained by compacting the powdery starting materials into component blanks or components.
  • Compacting processes such as sintering, hot isostatic pressing or injection molding make it possible to manufacture high-temperature-resistant, abrasion-resistant components.
  • Very dense, well adhering composite layers were produced by vacuum plasma spraying. They have been tested for corrosion resistance and adhesive strength by cyclical heating to 900 ° C and cooling to 200 ° C. The heating, tempering and cooling cycle lasted 80 minutes. A nickel-based superalloy was used as the base material.
  • Layers with different hard material contents were produced by powder plasma deposition welding and plasma spraying, and the abrasion wear behavior against SiC disks of 600 grit as the counter body was determined. All matrix-hard material combinations showed a similar behavior improved compared to the hard material-free matrix layer. The addition of 75% by volume of hard material results in a significant reduction in the wear rate, regardless of the type of hard material. Depending on the type of hard material, wear is only 55 to 70% of the wear rate of the pure matrix alloy.
  • MCrAlY-platinum-hard material composite powders have been processed into compact bodies by hot isostatic pressing (HIP).
  • HIP hot isostatic pressing

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Description

Die vorliegende Erfindung betrifft einen neuen korrosions- und verschleißbeständigen Hochtemperatur-Verbund-Werkstoff bestehend aus MCrAly-Matrixmetall, wobei M Fe, Co und/oder Ni bedeutet und Y gegebenenfalls fehlen kann, mit Platin und/oder Rhodium als Legierungselementen in Mengen von 5 bis 15 Gew.-%, Sowie aus in das Matrixmetall eingelagerten Hartstoffpartikeln, ein Verfahren zur Herstellung dieses Hochtemperatur-Verbund-Werkstoffes sowie dessen Verwendung.The present invention relates to a new corrosion and wear-resistant high-temperature composite material consisting of MCrAly matrix metal, where M is Fe, Co and / or Ni and Y may be absent, with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, as well as from hard material particles embedded in the matrix metal, a process for producing this high-temperature composite material and its use.

In vielen modernen Industrieanlagen, wie z.B. bei der Energiegewinnung, der Müllverbrennung oder Kohlevergasung, müssen Anlagen-Bauteile gegen Hochtemperaturkorrosion und Verschleiß beständig sein oder durch geeignete Überzüge weitgehend davor geschützt werden.In many modern industrial plants, e.g. In energy generation, waste incineration or coal gasification, system components must be resistant to high-temperature corrosion and wear or largely protected against them by suitable coatings.

Aus dem Bereich des Gasturbinenbaus, insbesondere der Flugtriebwerke, ist der Einsatz von Werkstoffen mit der allgemeinen Bezeichnung MCrAlY-Legierungen bekannt, wobei M ein Metall aus der Gruppe Eisen, Kobalt und Nickel oder Kombinationen dieser Elemente darstellt. Werkstoffe dieser Art sind beschrieben in den US-A-3 874 901, US-A-3 928 026, US-A-3 542 530 und US-A-3 754 903. Die Weiterentwicklung der MCrAlY-Legierungen mit dem Ziel, die Korrosionsbeständigkeit zu erhöhen, hat zu Edelmetallhaltigen Legierungstypen geführt. So wird in der US-A-3 918 139 eine MCrAlY-Legierung mit 3 bis 12 Gew.-% Platin oder Rhodium beschrieben, Platin-haltige Überzugslegierungen auf NiCrAl-Basis haben in der Vergangenheit in vielen Fällen hervorragende Korrosionsbeständigkeit bewiesen.The use of materials with the general designation MCrAlY alloys is known from the field of gas turbine construction, in particular aircraft engines, where M is a metal from the group of iron, cobalt and nickel or combinations of these elements. Materials of this type are described in US-A-3 874 901, US-A-3 928 026, US-A-3 542 530 and US-A-3 754 903. The further development of MCrAlY alloys with the aim of corrosion resistance has led to alloy types containing precious metals. For example, an MCrAlY alloy with 3 to 12% by weight of platinum or rhodium is described in US Pat. No. 3,918,139; platinum-containing NiCrAl-based coating alloys have proven excellent corrosion resistance in the past in many cases.

Zur Verbesserung des Verschleißverhaltens der MCrAlY-Werkstoffe können gemäß den US-A-3 879 831 und US-A-4 124 737 den Basislegierungen unter anderem Hartstoffe wie Oxide und Nitride zugesetzt werden, Darüber hinaus ist aus der US-A-4 275 124 bekannt, das Verschleißverhalten von MCrAlY-Legierungen durch in - situ - gebildete Carbide oder durch zulegierte Carbide zu erhöhen.In order to improve the wear behavior of the MCrAlY materials, hard materials such as oxides and nitrides can be added to the base alloys in accordance with US Pat. Nos. 3,879,831 and 4,124,737. In addition, US Pat. No. 4,275,124 known to increase the wear behavior of MCrAlY alloys by carbides formed in situ or by alloyed carbides.

In der US-A-4 275 090 ist Chromcarbid, Cr₃C₂, als Zusatz genannt. Außerdem ist aus den US-A-4 117 179 und US-A-4 124 737 der Zusatz von TaC zu Ni-Cr- und Co-Cr-Werkstoffen zwar bekannt, der Einfluß von Tantal auf das Oxidations-Korrosionsverhalten wird aber vorwiegend als negativ beschrieben.In US-A-4 275 090 chromium carbide, Cr₃C₂, is mentioned as an additive. In addition, the addition of TaC to Ni-Cr and Co-Cr materials is known from US Pat. Nos. 4,117,179 and 4,124,737, but the influence of tantalum on the oxidation-corrosion behavior is predominantly known as described negatively.

Die in die MCrAlY-Matrix eingelagerten Carbide reagieren aufgrund physikalischer und chemischer Eigenschaften dieses Verbundsystems unter den auftretenden Betriebstemperaturen mehr oder weniger stark in der Matrix. Die Reaktionsgeschwindigkeit nimmt mit steigender Temperatur zu und Carbide der 6. Nebengruppe (z.B. Cr₃C₂) werden bei gleicher Temperatur schneller abgebaut als die der 4. Nebengruppe (z,B. TiC, NbC). Da der Wirkungsgrad vieler bei hohen Temperaturen arbeitenden Anlagen durch Temperatursteigerung weiter erhöht werden kann, sind jedoch hochtemperaturstabile korrosions- und verschleißbeständige Werkstoffe erforderlich.The carbides embedded in the MCrAlY matrix react more or less strongly in the matrix due to the physical and chemical properties of this composite system under the operating temperatures that occur. The reaction rate increases with increasing temperature zu and carbides of the 6th subgroup (eg Cr₃C₂) are degraded faster at the same temperature than that of the 4th subgroup (e.g. TiC, NbC). Since the efficiency of many systems operating at high temperatures can be further increased by increasing the temperature, high-temperature stable, corrosion and wear-resistant materials are required.

Aufgabe der Erfindung ist es daher, die Hochtemperatur-Stabilität der Verbundwerkstoffe aus MCrAlY-Matrix und Hartstoffen zu verbessern, um die Nachteile der bekannten Werkstoff-Kombinationen zu überwinden. Demgemäß sollen also temperaturstabile korrosions- und verschleißbeständige Legierungen zur Verfügung gestellt werden, die bei Temperaturen von 600 bis 1100°C einsetzbar sind.The object of the invention is therefore to improve the high-temperature stability of the composite materials made of MCrAlY matrix and hard materials in order to overcome the disadvantages of the known material combinations. Accordingly, temperature-stable, corrosion-resistant and wear-resistant alloys should be made available, which can be used at temperatures of 600 to 1100 ° C.

Es wurde nun gefunden, daß diese Bedingungen erfüllt werden durch einen MCrAl(Y)-Werkstoff (mit oder ohne Yttrium-Anteil), der neben Platin oder Rhodium Carbide der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente enthält. Es hat sich gezeigt, daß diese zusätzlichen Legierungs-Elemente die Abbau-Reaktionen der Carbide mit der Matrix stark verringern, so daß in die Matrix eingelagerte Carbidpartikel ihre verschleißhemmende Wirkung länger aufrechterhalten. Der Einsatz von Mischcarbiden ist ebenfalls möglich.It has now been found that these conditions are met by an MCrAl (Y) material (with or without yttrium content) which, in addition to platinum or rhodium carbides, is the 4th and / or 5th and / or 6th subgroup of the periodic table Contains items. It has been shown that these additional alloy elements greatly reduce the degradation reactions of the carbides with the matrix, so that carbide particles embedded in the matrix maintain their wear-inhibiting effect for longer. Mixed carbides can also be used.

Die vom Platin zusätzlich ausgehende positive Wirkung in diesem Zusammenhang ist bekanntermaßen eine Verbesserung des Korrosionsverhaltens durch verbesserte Oxidhaftung auf der Oberfläche, Der Platingehalt der MCrAlY-Matrix kann bis zu 15 Gew.-% betragen, der Carbidanteil zwischen 0,01 und 75 Gew.-% variieren.The additional positive effect of platinum in this context is known to be an improvement in the corrosion behavior through improved oxide adhesion on the surface. The platinum content of the MCrAlY matrix can be up to 15% by weight, the carbide content between 0.01 and 75% by weight. % vary.

Gegenstand dieser Erfindung ist somit ein Korrosions- und verschleißbeständiger Hochtemperatur-Verbund-Werkstoff bestehend aus MCrAlY-Matrixmetall, wobei M Fe, Co und/oder Ni bedeutet und Y gegebenenfalls fehlen kann, mit Platin und/oder Rhodium als Legierungselemente in Mengen von 5 bis 15 Gew.-%, Sowie aus in das Matrixmetall eingelagerten Hartstoffpartikeln in Form von Carbiden der Elemente Vanadium, Niob, Tantal, Titan, Zirkon, Hafnium, Chrom, Molybdän und/oder Wolfram und/oder Mischungen derselben in Mengen von 0,01 bis 75 Gew.-%, bevorzugt 5 bis 75 Gew.-%, bezogen auf den Hochtemperatur-Verbund-Werkstoff.This invention thus relates to a corrosion and wear-resistant high-temperature composite material consisting of MCrAlY matrix metal, where M is Fe, Co and / or Ni and Y may be absent, with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, as well as from hard material particles embedded in the matrix metal in the form of carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof in quantities of 0.01 to 75% by weight, preferably 5 to 75% by weight, based on the high-temperature composite material.

In einer bevorzugten Ausführungsform beträgt die Carbid-Partikelgröße unter 50 µm. Die enthaltenen Carbid-Partikel sind kompakt. Entsprechende Matrixlegierungen des Typs MCrAlY mit Platin- und/oder Rhodiumzusätzen in Pulverform als Matrixwerkstoffe für Verbundwerkstoffe mit eindispergierten Hartstoffpulvern waren bislang noch nicht bekannt geworden.In a preferred embodiment, the carbide particle size is less than 50 μm. The carbide particles contained are compact. Corresponding matrix alloys of the MCrAlY type with platinum and / or rhodium additives in powder form as matrix materials for composite materials with dispersed hard material powders have hitherto not been disclosed.

Gegenstand dieser Erfindung ist auch ein Verfahren zur Herstellung der erfindungsgemäßen Hochtemperatur-Verbund-Werkstoffe. Die erfindungsgemäßen MCrAlY-Hartstoff-Legierungen können bevorzugt durch Suspensionsverdüsen, mechanisches Legieren oder Mischen von Verbundpulver aus MCrAlY, Platin und/oder Rhodium und Hartstoffen in Form von Carbiden der Elemente Vanadium, Niob, Tantal, Titan, Zirkon, Hafnium, Chrom, Molybdän und/oder Wolfram und/oder Mischungen derselben hergestellt werden, die 5 bis 15 Gew.-% Platin und/oder Rhodium und 0,01 bis 75 Gew.-%, bevorzugt 5 bis 75 Gew.-%, Metallcarbidanteil enthalten, erhalten werden.This invention also relates to a method for producing the high-temperature composite materials according to the invention. The MCrAlY hard alloys according to the invention can preferably by suspension spraying, mechanical alloying or mixing of composite powders of MCrAlY, platinum and / or rhodium and hard materials in the form of carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof, which are produced 5 to 15% by weight of platinum and / or rhodium and 0.01 to 75% by weight, preferably 5 to 75% by weight, containing metal carbide can be obtained.

Gegenstand der Erfindung ist auch die Verwendung der Hochtemperatur-Verbund-Werkstoffe zur Herstellung von Oberflächenschutzschichten. Hierbei erfolgt die Verarbeitung der Pulver zu den Oberflächenschutzschichten bevorzugt durch Auftragsschweiß- oder thermische Spritzverfahren wie Plasmaspritzen, Pulverplasma-Auftragsschweißen, Hochgeschwindigkeitsflammspritzen oder Laser-Beschichten.The invention also relates to the use of the high-temperature composite materials for the production of surface protective layers. Here, the powders are processed to form the surface protective layers, preferably by build-up welding or thermal spraying processes such as plasma spraying, powder plasma build-up welding, high-speed flame spraying or laser coating.

Gegenstand dieser Erfindung ist auch die Verwendung der erfindungsgemäßen Hochtemperatur-Verbund-Werkstoffe zur Herstellung von Kompaktbauteilen, die durch Kompaktieren der pulverförmigen Ausgangsstoffe zu Bauteilrohlingen oder Bauteilen erhalten werden. Durch Kompaktierverfahren wie Sintern, heißisostatisches Pressen oder Spritzguß ist die Herstellung hochtemperaturbeständiger, abriebfester Bauteile möglich.This invention also relates to the use of the high-temperature composite materials according to the invention for the production of compact components which are obtained by compacting the powdery starting materials into component blanks or components. Compacting processes such as sintering, hot isostatic pressing or injection molding make it possible to manufacture high-temperature-resistant, abrasion-resistant components.

Sehr dichte, gut haftende Verbundschichten wurden durch Vakuumplasmaspritzen hergestellt. Sie sind auf Korrosionsbeständigkeit und Haftfestigkeit durch zyklisches Aufheizen auf 900°C und Abkühlen auf 200°C getestet worden. Der Aufheiz-, Temper- und Abkühlzyklus dauerte 80 Minuten. Als Grundwerkstoff wurde eine Nickelbasis-Superlegierung verwendet.Very dense, well adhering composite layers were produced by vacuum plasma spraying. They have been tested for corrosion resistance and adhesive strength by cyclical heating to 900 ° C and cooling to 200 ° C. The heating, tempering and cooling cycle lasted 80 minutes. A nickel-based superalloy was used as the base material.

Nach 1000 Testzyklen (1333 Stunden) waren keine Anzeichen für einen Ausfall der Schichten - Durchbrüche oder Abplatzungen - zu erkennen.After 1000 test cycles (1333 hours) there were no signs of failure of the layers - breakthroughs or flaking.

Ein Vergleich zwischen platinfreier und platinhaltiger, mit Carbiden durchsetzter Matrix zeigt, daß der diffusionsbedingte Austausch zwischen Carbid- und Matrixelementen bei Anwesenheit von Platin langsamer abläuft.A comparison between a platinum-free and a platinum-containing matrix interspersed with carbides shows that the diffusion-related exchange between carbide and matrix elements takes place more slowly in the presence of platinum.

Durch Pulverplasmaauftragsschweißen und Plasmaspritzen wurden Schichten mit unterschiedlichen Gehalten an Hartstoffen hergestellt und damit das Abrasions-Verschleißverhalten gegen SiC-Scheiben der Körnung 600 als Gegenkörper ermittelt. Alle Matrix-Hartstoff-Kombinationen zeigten dabei ein ähnliches gegenüber der Hartstofffreien Matrix-Schicht verbessertes Verhalten. Die Zugabe von 75 Vol.-% Hartstoff bewirkt unabhängig von der Hartstoffart eine deutliche Verminderung der Verschleißrate. Je nach Hartstoffart beträgt der Verschleiß nur noch 55 bis 70 % der Verschleißrate der reinen Matrix-Legierung.Layers with different hard material contents were produced by powder plasma deposition welding and plasma spraying, and the abrasion wear behavior against SiC disks of 600 grit as the counter body was determined. All matrix-hard material combinations showed a similar behavior improved compared to the hard material-free matrix layer. The addition of 75% by volume of hard material results in a significant reduction in the wear rate, regardless of the type of hard material. Depending on the type of hard material, wear is only 55 to 70% of the wear rate of the pure matrix alloy.

MCrAlY-Platin-Hartstoff-Verbundpulver sind durch heißisostatisches Pressen (HIP) zu Kompaktkörpern verarbeitet worden. Die Auswertung von Verschleißuntersuchungen bestätigt die mit Hilfe der Schutzschicht gewonnenen Ergebnisse.MCrAlY-platinum-hard material composite powders have been processed into compact bodies by hot isostatic pressing (HIP). The evaluation of wear tests confirms the results obtained with the help of the protective layer.

Claims (4)

  1. A corrosion- and wear-resistant high-temperature composite material consisting of MCrAlY matrix metal, where M is Fe, Co and/or Ni and Y may optionally be absent, with platinum and/or rhodium as alloying elements in quantities of 5 to 15% by weight and of particles of hard material incorporated in the matrix metal in the form of carbides of the elements vanadium, niobium, tantalum, titanium, Zirconium, hafnium, chromium, molybdenum and/or tungsten and/or mixtures thereof in quantities of 0.01 to 75% by weight and preferably in quantities of 5 to 75% by weight, based on the high-temperature composite material.
  2. A process for the production of the high-temperature composite materials claimed in claim 1, characterized in that they are produced by suspension spraying, mechanical alloying or mixing of composite powders of MCrAlY, platinum and/or rhodium and hard materials in the form of carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and/or tungsten and/or mixtures thereof which contain 5 to 15% by weight platinum and/or rhodium and 0.01 to 75% by weight and preferably 5 to 75% by weight metal carbide.
  3. The use of the high-temperature composite materials claimed in claim 1 or 2 for the production of protective surface layers which are obtained by hard facing or by thermal spraying processes, such as plasma spraying, powder plasma hard facing, high-speed flame spraying or laser coating.
  4. The use of the high-temperature composite materials claimed in claim 1 or 2 for the production of compact components which are obtained by compacting of the powder-form starting materials to blanks or to the actual components.
EP90109913A 1989-06-06 1990-05-24 High temperature composite material, process for its manufacture and its use Expired - Lifetime EP0401611B1 (en)

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DE3918380A DE3918380A1 (en) 1989-06-06 1989-06-06 HIGH-TEMPERATURE COMPOSITE MATERIAL, METHOD FOR THE PRODUCTION AND USE THEREOF
DE3918380 1989-06-06

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EP0401611B1 true EP0401611B1 (en) 1993-11-24

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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK0522583T3 (en) * 1991-07-12 1995-09-25 Praxair Technology Inc Rotary contact gasket element coated with a chromium carbide-age-curable nickel-based alloy
US5712050A (en) * 1991-09-09 1998-01-27 General Electric Company Superalloy component with dispersion-containing protective coating
US5500252A (en) * 1992-09-05 1996-03-19 Rolls-Royce Plc High temperature corrosion resistant composite coatings
GB9218858D0 (en) * 1992-09-05 1992-10-21 Rolls Royce Plc High temperature corrosion resistant composite coatings
GB2276886B (en) * 1993-03-19 1997-04-23 Smith International Rock bits with hard facing
US5455119A (en) * 1993-11-08 1995-10-03 Praxair S.T. Technology, Inc. Coating composition having good corrosion and oxidation resistance
US5765624A (en) * 1994-04-07 1998-06-16 Oshkosh Truck Corporation Process for casting a light-weight iron-based material
TW383233B (en) * 1995-01-31 2000-03-01 Rieter Ag Maschf Thread guiding elements
GB2319783B (en) * 1996-11-30 2001-08-29 Chromalloy Uk Ltd A thermal barrier coating for a superalloy article and a method of application thereof
FR2757181B1 (en) * 1996-12-12 1999-02-12 Snecma PROCESS FOR PRODUCING A HIGH EFFICIENCY PROTECTIVE COATING AGAINST HIGH TEMPERATURE CORROSION FOR SUPERALLOYS, PROTECTIVE COATING OBTAINED BY THIS PROCESS AND PARTS PROTECTED BY THIS COATING
JPH11343564A (en) * 1998-05-28 1999-12-14 Mitsubishi Heavy Ind Ltd High temperature equipment
DE10111111C2 (en) * 2001-03-08 2003-11-27 Deutsche Titan Gmbh Method of making a plate armored against shelling and splinters
EP1365044A1 (en) * 2002-05-24 2003-11-26 Siemens Aktiengesellschaft MCrAl-coating
US7316850B2 (en) * 2004-03-02 2008-01-08 Honeywell International Inc. Modified MCrAlY coatings on turbine blade tips with improved durability
US7378132B2 (en) * 2004-12-14 2008-05-27 Honeywell International, Inc. Method for applying environmental-resistant MCrAlY coatings on gas turbine components
DE102005044991A1 (en) * 2005-09-21 2007-03-22 Mtu Aero Engines Gmbh Process for producing a protective layer, protective layer and component with a protective layer
DE102006060776A1 (en) * 2006-12-21 2008-06-26 Siemens Ag Component e.g. for drilling machine for drilling into geological rock formation, has drilling machine having compatible base body with coating provided and ductile metal base material embedded with hard material particles
JP5058645B2 (en) * 2007-03-27 2012-10-24 トーカロ株式会社 Thermal spray powder, thermal spray coating and hearth roll
US8268237B2 (en) * 2009-01-08 2012-09-18 General Electric Company Method of coating with cryo-milled nano-grained particles
US8708659B2 (en) 2010-09-24 2014-04-29 United Technologies Corporation Turbine engine component having protective coating
US8544769B2 (en) 2011-07-26 2013-10-01 General Electric Company Multi-nozzle spray gun
CN108486522A (en) * 2018-06-26 2018-09-04 中国科学院金属研究所 A kind of catalytic cracking unit valve wear-and corrosion-resistant coating and preparation method thereof
EP3863990A4 (en) 2018-10-09 2022-10-12 Oerlikon Metco (US) Inc. High-entropy oxides for thermal barrier coating (tbc) top coats
CN115747795B (en) * 2022-12-05 2024-03-26 江苏大学 Thermal barrier coating bonding layer with high service life and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3802938A (en) * 1973-03-12 1974-04-09 Trw Inc Method of fabricating nickel base superalloys having improved stress rupture properties
US3918139A (en) * 1974-07-10 1975-11-11 United Technologies Corp MCrAlY type coating alloy
DE2842848C2 (en) * 1977-10-17 1987-02-26 United Technologies Corp., Hartford, Conn. Material for covering objects
US4275124A (en) * 1978-10-10 1981-06-23 United Technologies Corporation Carbon bearing MCrAlY coating
US4275090A (en) * 1978-10-10 1981-06-23 United Technologies Corporation Process for carbon bearing MCrAlY coating
US4439470A (en) * 1980-11-17 1984-03-27 George Kelly Sievers Method for forming ternary alloys using precious metals and interdispersed phase
CH647818A5 (en) * 1980-12-05 1985-02-15 Castolin Sa POWDERED COATING MATERIAL FOR THERMAL COATING OF WORKPIECES.

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CA2018254A1 (en) 1990-12-06
KR910001079A (en) 1991-01-30
DE59003581D1 (en) 1994-01-05
JPH0344456A (en) 1991-02-26
US5141821A (en) 1992-08-25
DE3918380A1 (en) 1990-12-20

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