EP0401611A1 - 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

Info

Publication number
EP0401611A1
EP0401611A1 EP90109913A EP90109913A EP0401611A1 EP 0401611 A1 EP0401611 A1 EP 0401611A1 EP 90109913 A EP90109913 A EP 90109913A EP 90109913 A EP90109913 A EP 90109913A EP 0401611 A1 EP0401611 A1 EP 0401611A1
Authority
EP
European Patent Office
Prior art keywords
weight
temperature composite
platinum
rhodium
mcraly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90109913A
Other languages
German (de)
French (fr)
Other versions
EP0401611B1 (en
Inventor
Erich Prof. Dr. Lugscheider
Heinz Prof Dr. Eschnauer
Johannes Dr. Wilden
Frank Dipl.-Phys Büche
Helmut Dr. Meinhardt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HC Starck GmbH
Original Assignee
HC Starck GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HC Starck GmbH filed Critical HC Starck GmbH
Publication of EP0401611A1 publication Critical patent/EP0401611A1/en
Application granted granted Critical
Publication of EP0401611B1 publication Critical patent/EP0401611B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • 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
    • 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
    • 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
    • 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-resistant and wear-resistant high-temperature composite material based on an alloy of the type MCrAlY as matrix metal with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, a method 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-53 928 026, US-A-3 542 530 and US-A-3 754 903.
  • MCrAlY alloys with the aim of corrosion resistance to increase 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 many cases in the past.
  • 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. It is also known from US Pat. No. 4,275,124 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 broken down faster at the same temperature than that of the 4th subgroup (eg TiC, NbC). Since the efficiency of many systems operating at high temperatures can be increased further 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.
  • 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 can vary between 0.01 and 75% by weight.
  • This invention thus relates to a corrosion-resistant and wear-resistant high-temperature composite material based on an alloy of the type MCrAlY as a matrix metal with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, with hard material particles in the form of the matrix metal carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof in amounts 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 such as carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof, which are produced from 5 to 15% by weight of platinum and / or rhodium and 0.01 to 75% by weight, preferably 5 to 75% by weight, of metal carbide content 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 means of 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. 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

Landscapes

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

Abstract

The present invention relates to a novel corrosion-resistant and wear-resistant high-temperature composite material based on an alloy of the type MCrAlY as a matrix metal with platinum and/or rhodium as alloy elements in amounts of 5 to 15 % by weight, a process for the production of this high-temperature composite material and its use.

Description

Die vorliegende Erfindung betrifft einen neuen korro­sions- und verschleißbeständigen Hochtemperatur-Verbund-­Werkstoff auf Basis einer Legierung des Typs MCrAlY als Matrixmetall mit Platin und/oder Rhodium als Legierungs­elemente in Mengen von 5 bis 15 Gew.-%, ein Verfahren zur Herstellung dieses Hochtemperatur-Verbund-Werkstof­fes sowie dessen Verwendung.The present invention relates to a new corrosion-resistant and wear-resistant high-temperature composite material based on an alloy of the type MCrAlY as matrix metal with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, a method 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-­53 928 026, 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-53 928 026, US-A-3 542 530 and US-A-3 754 903. The further development of MCrAlY alloys with the aim of corrosion resistance to increase 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 many cases in the past.

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.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. It is also known from US Pat. No. 4,275,124 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-­4 124 137 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. No. 4,117,179 and US Pat. No. 4,124,137, 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 broken down faster at the same temperature than that of the 4th subgroup (eg TiC, NbC). Since the efficiency of many systems operating at high temperatures can be increased further 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 portion) 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 decomposition reactions of the carbides with the matrix, so that carbide particles embedded in the matrix maintain their wear-inhibiting effect for longer. The use of mixed carbides is also possible.

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 can vary between 0.01 and 75% by weight.

Gegenstand dieser Erfindung ist somit ein Korrosions- und verschleißbeständiger Hochtemperatur-Verbund-Werk­stoff auf Basis einer Legierung des Typs MCrAlY als Matrixmetall mit Platin und/oder Rhodium als Legierungs­elemente in Mengen von 5 bis 15 Gew.-%, wobei in das Ma­trixmetall Hartstoffpartikel 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, eingelagert sind.This invention thus relates to a corrosion-resistant and wear-resistant high-temperature composite material based on an alloy of the type MCrAlY as a matrix metal with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, with hard material particles in the form of the matrix metal carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof in amounts 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 wie 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 such as carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof, which are produced from 5 to 15% by weight of platinum and / or rhodium and 0.01 to 75% by weight, preferably 5 to 75% by weight, of metal carbide content 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 means of 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 wor­ den. 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. 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. Korrosions- und verschleißbeständiger Hochtempera­tur-Verbund-Werkstoff auf Basis einer Legierung des Typs MCrAlY als Matrixmetall mit Platin und/oder Rhodium als Legierungselemente in Mengen von 5 bis 15 Gew.-%, dadurch gekennzeichnet, daß in das Ma­trixmetall Hartstoffpartikel 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, eingelagert sind.1. Corrosion and wear-resistant high-temperature composite material based on an alloy of the type MCrAlY as a matrix metal with platinum and / or rhodium as alloying elements in amounts of 5 to 15% by weight, characterized in that hard material particles in the form of Carbides of the elements vanadium, niobium, tantalum, titanium, zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof in amounts of 0.01 to 75% by weight, preferably 5 to 75% by weight, based on the high-temperature composite material. 2. Verfahren zur Herstellung von Hochtemperatur-Ver­bund-Werkstoffen gemäß Anspruch 1, dadurch gekenn­zeichnet, daß durch Suspensionsverdüsen, mechani­sches Legieren oder Mischen von Verbundpulver aus MCrAlY, Platin und/oder Rhodium und Hartstoffen wie 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.2. A method for producing high-temperature composite materials according to claim 1, characterized in that by suspension spraying, mechanical alloying or mixing of composite powders made of MCrAlY, platinum and / or rhodium and hard materials such as carbides of the elements vanadium, niobium, tantalum, titanium, Zirconium, hafnium, chromium, molybdenum and / or tungsten and / or mixtures thereof are produced which contain 5 to 15% by weight of platinum and / or rhodium and 0.01 to 75% by weight, preferably 5 to 75% by weight. %, Contain metal carbide. 3. Verwendung der Hochtemperatur-Verbund-Werkstoffe gemäß einem der Ansprüche 1 oder 2 zur Herstellung von Oberflächenschutzschichten, die durch Auftrags­schweiß- oder thermische Spritzverfahren wie Plas­ maspritzen, Pulverplasma-Auftragsschweißen, Hochge­schwindigkeitsflammspritzen oder Laser-Beschichten erhalten werden.3. Use of the high-temperature composite materials according to one of claims 1 or 2 for the production of surface protective layers, which by plating or thermal spraying processes such as plas spraying, powder plasma deposition welding, high-speed flame spraying or laser coating can be obtained. 4. Verwendung der Hochtemperatur-Verbund-Werkstoffe gemäß einem der Ansprüche 1 oder 2 zur Herstellung von Kompaktbauteilen, die durch Kompaktieren der pulverförmigen Ausgangsstoffe zu Bauteilrohlingen oder Bauteilen erhalten werden.4. Use of the high-temperature composite materials according to one of claims 1 or 2 for the production of compact components, which are obtained by compacting the powdery starting materials into component blanks or components.
EP90109913A 1989-06-06 1990-05-24 High temperature composite material, process for its manufacture and its use Expired - Lifetime EP0401611B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3918380A DE3918380A1 (en) 1989-06-06 1989-06-06 HIGH-TEMPERATURE COMPOSITE MATERIAL, METHOD FOR THE PRODUCTION AND USE THEREOF
DE3918380 1989-06-06

Publications (2)

Publication Number Publication Date
EP0401611A1 true EP0401611A1 (en) 1990-12-12
EP0401611B1 EP0401611B1 (en) 1993-11-24

Family

ID=6382146

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90109913A Expired - Lifetime EP0401611B1 (en) 1989-06-06 1990-05-24 High temperature composite material, process for its manufacture and its use

Country Status (6)

Country Link
US (1) US5141821A (en)
EP (1) EP0401611B1 (en)
JP (1) JPH0344456A (en)
KR (1) KR910001079A (en)
CA (1) CA2018254A1 (en)
DE (2) DE3918380A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0652299A1 (en) * 1993-11-08 1995-05-10 ROLLS-ROYCE plc Coating composition having good corrosion and oxidation resistance
US5897947A (en) * 1995-01-31 1999-04-27 Maschinenfabrik Rieter Ag Method of coating and thread guiding elements produced thereby
EP0961017A2 (en) * 1998-05-28 1999-12-01 Mitsubishi Heavy Industries, Ltd. High temperature resistant coating

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2785087B2 (en) * 1991-07-12 1998-08-13 プラクセア・エス・ティー・テクノロジー・インコーポレイテッド Rotary seal member coated with chromium carbide-age-hardenable 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
US5765624A (en) * 1994-04-07 1998-06-16 Oshkosh Truck Corporation Process for casting a light-weight iron-based material
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
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
WO2020142125A2 (en) 2018-10-09 2020-07-09 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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1500780A (en) * 1974-07-10 1978-02-08 United Technologies Corp Mcraly type coating alloy
GB2006274A (en) * 1977-10-17 1979-05-02 United Technologies Corp Oxidation and Wear Resistant Coated Article
US4275124A (en) * 1978-10-10 1981-06-23 United Technologies Corporation Carbon bearing MCrAlY coating
WO1982001897A1 (en) * 1980-12-05 1982-06-10 Simm Wolfgang Material allowing the stratification of machining parts,the latter having then an improved resistance to abrasion and hammering

Family Cites Families (3)

* 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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1500780A (en) * 1974-07-10 1978-02-08 United Technologies Corp Mcraly type coating alloy
GB2006274A (en) * 1977-10-17 1979-05-02 United Technologies Corp Oxidation and Wear Resistant Coated Article
US4275124A (en) * 1978-10-10 1981-06-23 United Technologies Corporation Carbon bearing MCrAlY coating
WO1982001897A1 (en) * 1980-12-05 1982-06-10 Simm Wolfgang Material allowing the stratification of machining parts,the latter having then an improved resistance to abrasion and hammering

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0652299A1 (en) * 1993-11-08 1995-05-10 ROLLS-ROYCE plc Coating composition having good corrosion and oxidation resistance
US5897947A (en) * 1995-01-31 1999-04-27 Maschinenfabrik Rieter Ag Method of coating and thread guiding elements produced thereby
EP0961017A2 (en) * 1998-05-28 1999-12-01 Mitsubishi Heavy Industries, Ltd. High temperature resistant coating
EP0961017A3 (en) * 1998-05-28 2001-03-14 Mitsubishi Heavy Industries, Ltd. High temperature resistant coating
US6548161B1 (en) 1998-05-28 2003-04-15 Mitsubishi Heavy Industries, Ltd. High temperature equipment

Also Published As

Publication number Publication date
DE3918380A1 (en) 1990-12-20
JPH0344456A (en) 1991-02-26
CA2018254A1 (en) 1990-12-06
KR910001079A (en) 1991-01-30
EP0401611B1 (en) 1993-11-24
US5141821A (en) 1992-08-25
DE59003581D1 (en) 1994-01-05

Similar Documents

Publication Publication Date Title
EP0401611B1 (en) High temperature composite material, process for its manufacture and its use
EP2753722B1 (en) Cermet powder
DE69104568T2 (en) Process for applying abrasion-resistant layers on blade surfaces.
DE60005416T2 (en) Thermal spray coating for valve seats and valve slide
DE2801016C2 (en) Article made from a superalloy body with a coating of a powder applied by flame spraying and a process for its production
DE69917834T2 (en) Powder of chromium carbide and nickel-chromium
DE2920198C2 (en) Powder for application to a metal substrate to form a coating with high wear and corrosion resistance
DE2758618C3 (en) Means for the production of a very high penaltype> estiindi8en · abrasion-resistant coating
DE3785424T2 (en) Wear body and powder as well as manufacturing processes.
DE69116303T2 (en) Manufacture of chromium carbide nickel coatings
DE3511220C2 (en)
DE3110358C2 (en) Powder coating agent and method for applying surface coatings
DE1521369C3 (en) Powdery, self-flowing flame spraying compound
WO2004074535A2 (en) Composite material consisting of intermetallic phases and ceramics and production method for said material
DE2604960A1 (en) MATERIAL AND PROCESS FOR MANUFACTURING OVERCOATING
DE60111565T2 (en) Method of making a metal matrix composite and metal matrix composite
DE2640741C2 (en) Sealing part in gas turbines
EP0044351A1 (en) Hard alloy consisting of one or several hard substances and a binding metal alloy, and process for producing this alloy
DE2842848A1 (en) COVERED OBJECT, IN PARTICULAR SUPER ALLOY GAS TURBINE BLADE
EP0948659B1 (en) Coating powder and method for its production
DE3036206A1 (en) WEAR-RESISTANT COATING, OXIDATION AND CORROSION PROTECTIVE COATING, CORROSION- AND WEAR-RESISTANT COATING ALLOY, ITEM PROVIDED WITH SUCH A COATING AND METHOD FOR PRODUCING SUCH A COATING
CH616960A5 (en) Components resistant to high-temperature corrosion.
DE102016114533A1 (en) Iron-based alloy for the production of thermally sprayed wear-resistant coatings
DE263427T1 (en) METAL-CERAMIC COMPOSITE MATERIAL AND METHOD FOR THE PRODUCTION THEREOF.
DE3590031T (en) Material for flame spraying and its manufacturing process

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19900531

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: H.C. STARCK GMBH & CO. KG

17Q First examination report despatched

Effective date: 19921006

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL SE

REF Corresponds to:

Ref document number: 59003581

Country of ref document: DE

Date of ref document: 19940105

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940222

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940414

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19940419

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940516

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940527

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19940531

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 90109913.5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19950525

ITTA It: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19951201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950524

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19951201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960201

EUG Se: european patent has lapsed

Ref document number: 90109913.5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960229

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050524