DE3229285C2 - - Google Patents

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Publication number
DE3229285C2
DE3229285C2 DE3229285A DE3229285A DE3229285C2 DE 3229285 C2 DE3229285 C2 DE 3229285C2 DE 3229285 A DE3229285 A DE 3229285A DE 3229285 A DE3229285 A DE 3229285A DE 3229285 C2 DE3229285 C2 DE 3229285C2
Authority
DE
Germany
Prior art keywords
hafnium
yttrium
coverings
gas turbine
superalloy
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.)
Expired
Application number
DE3229285A
Other languages
German (de)
Other versions
DE3229285A1 (en
Inventor
David Scott Cobalt Conn. Us Duvall
Dinesh Kumar Vernon Conn. Us Gupta
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.)
Raytheon Technologies Corp
Original Assignee
United Technologies Corp
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 United Technologies Corp filed Critical United Technologies Corp
Publication of DE3229285A1 publication Critical patent/DE3229285A1/en
Application granted granted Critical
Publication of DE3229285C2 publication Critical patent/DE3229285C2/de
Granted legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material
    • C23C4/073Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/52Alloys
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00After-treatment of single crystals or homogeneous polycrystalline material with defined structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Physical Vapour Deposition (AREA)

Description

Die Erfindung betrifft ein Gasturbinenbauteil aus einer Superlegierung auf Nickelbasis, das eine durch Aufbrin­ gen eines Schutzbelags verbesserte Oxidationsbeständig­ keit aufweist.The invention relates to a gas turbine component from a Super alloy based on nickel, one by applying improved oxidation resistance against a protective coating ability.

Es ist bekannt, Gasturbinenbauteile aus einer Superle­ gierung auf Nickelbasis dadurch hinsichtlich ihrer Oxi­ dationsbeständigkeit und Beständigkeit gegen Heißkorrosion zu verbessern, daß auf die Gasturbinenbauteile Deckbeläge aufgebracht werden, die aus Belagzusammensetzungen des NiCrAlY- und NiCoCrAlY-Typs (= MCrAlY-Typs) erzeugt werden. Diese Beläge wirken schützend, weil sie eine dünne Aluminiumoxidschicht auf ihrer Außenoberfläche aus­ bilden und diese auch wiederholt nachbilden können. Diese Aluminiumoxidschicht widersteht einem Angriff durch Oxi­ dation und Heißkorrosion. Sauerstoffaktive Elemente, wie z. B. Yttrium, werden den Belägen zugegeben, um die Haf­ tung des Aluminiumoxids zu verbessern und seine Neigung zum Abblättern zu hemmen.It is known to make gas turbine components from a superle nickel-based alloy in terms of their oxi dation resistance and resistance to hot corrosion to improve that on the gas turbine components decking be applied, which from the topping compositions of NiCrAlY and NiCoCrAlY type (= MCrAlY type) generated will. These rubbers are protective because they are one thin aluminum oxide layer on its outer surface form and can reproduce them repeatedly. These Aluminum oxide layer resists attack by oxi dation and hot corrosion. Oxygen active elements, such as e.g. B. yttrium, the coatings are added to the Haf alumina and improve its tendency to inhibit peeling.

MCrAlY-Deckbeläge sind in den US-PSen 35 42 530, 36 76 085, 37 54 903 und 39 28 026 sowie der DE-OS 25 28 241 beschrieben.MCrAlY coverings are in US Pat. Nos. 35 42 530, 36 76 085, 37 54 903 and 39 28 026 and DE-OS 25 28 241.

Wie ferner in der US-PS 37 11 337 beschrieben ist, war es bekannt, Superlegierungen, die in richtungsverfestigter Form verwendet werden sollten, kleine Mengen Hafnium (0,5 bis 2% Hafnium) zuzusetzen, um die Korngrenzen zu ver­ festigen.As further described in US Pat. No. 3,711,337 was it is known superalloys that are directionally hardened Form should be used, small amounts of hafnium (0.5 up to 2% hafnium) to adjust the grain boundaries consolidate.

Brachte man auf derartige richtungsverfestigte, Hafnium enthaltende Superlegierungssubstrate mit säulenförmigen Körnern MCrAlY-Deckbeläge auf, wurde gefunden, daß Yttrium in Mengen von mehr als ungefähr 0,5 oder 0,7 Gew.-% im Deckbelag zu unerwünscht niedrigschmelzenden Phasen an der Belag/Substrat-Grenzfläche führte, wobei diese Phasen offensichtlich auf Yttrium und Hafnium basierten.One brought to such directionally hardened, hafnium containing superalloy substrates with columnar Grains on MCrAlY coverings, it was found that yttrium in amounts greater than about 0.5 or 0.7 weight percent Covering to undesirably low-melting phases the topping / substrate interface resulted in these phases  obviously based on yttrium and hafnium.

Später wurde von richtungsverfestigten Superlegierungs­ gegenständen auf Einkristallgegenstände übergegangen, die frei von inneren Korngrenzen sind und deshalb nicht die Duktilitätsschwächen in Querrichtung aufweisen, die richtungsverfestigte Superlegierungen kennzeichnen. Bei Einkristallgegenständen war daher die Anwesenheit von Hafnium zur Korngrenzenfestigung nicht erforderlich, und da Hafnium die Warmbearbeitbarkeit von Gegenständen aus Einkristallsuperlegierungen verschlechterte, wurde bei derartigen Gegenständen Hafnium weggelassen. Deckbeläge, die für Einkristallsuperlegierungen entwickelt wurden, waren daher Deckbeläge für hafniumfreie Substratmaterialien.Later, directional strengthened superalloy objects transferred to single crystal objects, that are free from internal grain boundaries and therefore not which have transverse ductility weaknesses mark directionally hardened superalloys. At Single crystal objects was therefore the presence of Hafnium is not required for grain boundary strengthening, and because hafnium is the hot workability of objects Single crystal superalloys deteriorated such articles hafnium omitted. Coverings, developed for single crystal superalloys were therefore coverings for hafnium-free substrate materials.

Die nominellen Yttriumgehalte in den Deckbelägen bei­ spielsweise gemäß DE-OS 25 28 241 und US-PS 36 76 085 lagen im Bereich von 0,01 bis 2,0% bzw. von 0,01 bis 5 % Yttrium. Aufgrund der bekannten schädlichen Wechsel­ wirkung von Hafniumanteilen im Substratmaterial und Yttriumanteilen über 0,7% in Deckbelägen wurde dabei angenommen, daß Deckbeläge mit höheren Yttriumgehalten für hafniumhaltige Substrate ungeeignet sind.The nominal yttrium contents in the coverings for example according to DE-OS 25 28 241 and US-PS 36 76 085 ranged from 0.01 to 2.0% or from 0.01 to 5% yttrium. Because of the known harmful changes effect of hafnium in the substrate material and Yttrium contents over 0.7% in coverings were included assumed that coverings with higher yttrium contents are unsuitable for substrates containing hafnium.

Als im Rahmen der Entwicklung der vorliegenden Erfindung festgestellt wurde, daß Yttriumgehalte, die über den bisher üblichen Werten lagen, nämlich Yttriumgehalte im Bereich von 1,1 bis 3,0%, die Oxidationsbeständig­ keit von Belägen auf hafniumfreien Superlegierungs­ substraten verbesserten, mußte angenommen werden, daß eine derartige Verbesserung im Falle von hafniumhalti­ gen Substraten wegen der bekannten Ausbildung niedrig­ schmelzender Phasen nicht erreichbar wäre. Gasturbinen­ bauteile mit einem Gehalt an Hafnium konnten daher an­ scheinend nicht mit den an sich eine sehr gute Oxidations­ beständigkeit verleihenden MCrAlY-Belägen mit höheren Yttriumgehalten versehen werden. As part of the development of the present invention it was found that yttrium levels above the The usual values to date were yttrium contents in the range of 1.1 to 3.0%, the oxidation resistant of coatings on hafnium-free superalloy substrates, it had to be assumed that such an improvement in the case of hafniumhalti low substrates because of the known training melting phases would not be achievable. Gas turbines Components with a content of hafnium could therefore apparently not with a very good oxidation in itself resistance-giving MCrAlY coverings with higher Be provided with yttrium.  

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Superlegierungsgegenstände zu schaffen, die einerseits im Substrat Hafnium enthalten, deren Oxidationsbeständig­ keit jedoch andererseits durch Aufbringung eines Deck­ belags verbessert werden konnte.The present invention is based on the object To create superalloy objects on the one hand Contain hafnium in the substrate, whose oxidation resistance on the other hand, by applying a deck could be improved.

Diese Aufgabe wird durch Gasturbinenbauteile gemäß Patent­ anspruch 1 gelöst.This task is accomplished by gas turbine components according to the patent Claim 1 solved.

Vorteilhafte Ausgestaltungen sind den Unteransprüchen zu entnehmen.Advantageous configurations are the subclaims refer to.

Überraschenderweise wurde festgestellt, daß dann, wenn ein Deckbelag mit einer Belagzusammensetzung aus 10 bis 35% Cr, 8 bis 20% Al, 1,1 bis 3,0% Y, 0 bis 30% Co und im übrigen aus Nickel auf eine Superlegierung mit absicht­ lichen Hf-Zugaben von 0,1 bis 2% durch Plasmaspritzen aufgebracht wird, ein derartiges Gasturbinenbauteil eine erheblich verbesserte Oxidationsbeständigkeit aufweist. Das war angesichts der Tatsache überraschend, daß es bekannt war, daß sich beim Aufdampfen von Deckbelägen mit hohem Yttriumgehalt auf Hafnium enthaltende Substrate an der Substrat/Belag-Grenzfläche niedrigschmelzende Phasen aus­ bilden. Beläge, die durch ein Plasmaspritzverfahren aufge­ bracht worden sind, enthalten jedoch unverändert eine be­ trächtliche Menge Sauerstoff, der das Hafnium im Substrat oxidiert, welche sich in der Nähe der Belag/Substrat-Grenz­ fläche befindet. Wenn das Hafnium einmal oxidiert ist, dann ist es stabil und bildet keine schädlichen niedrigschmelzen­ den Phasen. Im Gegensatz zu MCrAlY-Belägen, die durch Dampf­ abscheidung aufgebracht wurden, hat die Abscheidung von Belagzusammensetzungen der im Patentanspruch genannten Art durch Plasmaspritzen auf 0,1 bis 2% Hafnium enthal­ tende Superlegierungssubstrate keine Schmelzpunktprobleme zur Folge.Surprisingly, it was found that when a Covering with a covering composition of 10 to 35% Cr, 8 to 20% Al, 1.1 to 3.0% Y, 0 to 30% Co and im Others made of nickel on a superalloy on purpose Hf additions of 0.1 to 2% by plasma spraying is applied, such a gas turbine component has significantly improved resistance to oxidation. This was surprising given the fact that it was known was that with the evaporation of coverings with high Yttrium content on substrates containing hafnium on the Low melting phases of the substrate / covering interface form. Coverings applied by a plasma spraying process have been brought, but still contain a be considerable amount of oxygen that the hafnium in the substrate oxidized, which is close to the surface / substrate boundary area located. Once the hafnium is oxidized, then it is stable and does not form harmful low melts the phases. In contrast to MCrAlY coverings caused by steam deposition has been applied, the deposition of Covering compositions of those mentioned in the claim Contain by plasma spraying to 0.1 to 2% hafnium superalloy substrates no melting point problems result.

Wenn übliche MCrAlY-Beläge mit Yttriumgehalten unter 1,1% durch Dampfabscheidung auf hafniumhaltige Substrate aufgebracht werden, dann diffundiert Hafnium aus dem Substrat in den Belag und verbessert dessen Verhalten. Wenn derartige MCrAlY-Beläge durch Plasmaspritzen auf hafniumhaltige Substrate aufgebracht werden, dann ver­ hindert der Sauerstoff, der als Yttrium- und Aluminium­ oxid im Belag vorliegt, daß das Hafnium ausreichend zur Grenzfläche des Belags diffundiert, um dessen Ver­ halten zu verbessern. Das diffundierte Hafnium redu­ ziert im Gegenteil die anderen Oxide (Aluminiumoxid und Yttriumoxid) und bildet stabile Hafniumoxide, was zur Folge hat, daß keine Verbesserung des Belags erreicht wird.If usual MCrAlY coverings with yttrium contents below 1.1%  by vapor deposition on substrates containing hafnium applied, then hafnium diffuses from the Substrate in the covering and improves its behavior. If such MCrAlY coverings by plasma spraying hafnium-containing substrates are applied, then ver prevents the oxygen acting as yttrium and aluminum oxide in the coating is present that the hafnium is sufficient diffused to the surface of the covering in order to ver keep improving. The diffused hafnium redu on the contrary, adorns the other oxides (aluminum oxide and Yttrium oxide) and forms stable hafnium oxides, which leads to The consequence is that the surface does not improve becomes.

Indem erfindungsgemäß ein an Yttrium reicher Belag mit einem Yttriumgehalt von 1,1 bis 3,0% Yttrium durch Plasmaspritzen aufgebracht wird, ist es möglich, die Sauerstoffverluste zu kompensieren, die durch den Effekt des Hafniums im Substrat im Deckbelag auftreten. Das zusätzliche Yttrium springt für das fehlende Hafnium ein und fördert eine gute Haftung der schützenden Alu­ miniumschicht des Belags. Durch Plasmaspritzen eines relativ yttriumreichen Deckbelags läßt sich somit auch die Dauerhaftigkeit hafniumhaltiger Substrate verbessern.By according to the invention a coating rich in yttrium a yttrium content of 1.1 to 3.0% yttrium Plasma spraying is applied, it is possible to Compensate for oxygen losses caused by the effect of hafnium in the substrate in the top layer. The additional yttrium jumps for the missing hafnium and promotes good adhesion of the protective aluminum minimum layer of the covering. By plasma spraying one relatively yttrium-rich coverings can also be used improve the durability of substrates containing hafnium.

Claims (3)

1. Gasturbinenbauteil aus einer Superlegierung auf Nickelbasis, das eine durch Aufbringen eines Schutzbelags verbesserte Oxi­ dationsbeständigkeit aufweist, dadurch gekennzeichnet, daß die Superlegierung absichtliche Hf-Zugaben von 0,1 bis 2% enthält und eine Belagzusammensetzung, die aus 10 bis 35% Cr, 8 bis 20% Al, 1,1 bis 3,0% Y, 0 bis 30% Co und im übrigen aus Nickel besteht, durch Plasmaspritzen aufgebracht ist.1. Gas turbine component made of a nickel-based superalloy which has an oxidation resistance which is improved by applying a protective coating, characterized in that the superalloy contains deliberate additions of 0.1 to 2% of Hf and a coating composition which consists of 10 to 35% Cr, 8 to 20% Al, 1.1 to 3.0% Y, 0 to 30% Co and otherwise made of nickel, is applied by plasma spraying. 2. Gasturbinenbauteil nach Anspruch 1, dadurch gekennzeichnet, daß die Superlegierung in Form eines Einkristallgegenstands vorliegt.2. Gas turbine component according to claim 1, characterized in that that the superalloy is in the form of a single crystal object is present. 3. Gasturbinenbauteil nach Anspruch 1 oder 2, dadurch gekenn­ zeichnet, daß der aufgebrachte Belag aus 15 bis 25% Cr, 10 bis 20% Al, 1,1 bis 3,0% Y, 15 bis 25% Co und im übrigen aus Nickel besteht.3. Gas turbine component according to claim 1 or 2, characterized shows that the applied coating consists of 15 to 25% Cr, 10 up to 20% Al, 1.1 to 3.0% Y, 15 to 25% Co and the rest consists of nickel.
DE19823229285 1981-08-05 1982-08-05 COATING COMPOSITION FOR PRODUCING A PROTECTIVE COATING ON SUBSTRATES FROM A SUPER ALLOY Granted DE3229285A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US28995381A 1981-08-05 1981-08-05

Publications (2)

Publication Number Publication Date
DE3229285A1 DE3229285A1 (en) 1983-03-24
DE3229285C2 true DE3229285C2 (en) 1988-11-24

Family

ID=23113894

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19823229285 Granted DE3229285A1 (en) 1981-08-05 1982-08-05 COATING COMPOSITION FOR PRODUCING A PROTECTIVE COATING ON SUBSTRATES FROM A SUPER ALLOY

Country Status (6)

Country Link
JP (1) JPS5837146A (en)
CA (1) CA1209827A (en)
DE (1) DE3229285A1 (en)
FR (1) FR2511043B1 (en)
GB (1) GB2103656B (en)
IL (1) IL66443A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005053531A1 (en) * 2005-11-08 2007-05-10 Man Turbo Ag Heat-insulating protective layer for a component within the hot gas region of a gas turbine

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US4743514A (en) * 1983-06-29 1988-05-10 Allied-Signal Inc. Oxidation resistant protective coating system for gas turbine components, and process for preparation of coated components
US4677035A (en) * 1984-12-06 1987-06-30 Avco Corp. High strength nickel base single crystal alloys
DE3612568A1 (en) * 1986-04-15 1987-10-29 Bbc Brown Boveri & Cie HIGH TEMPERATURE PROTECTIVE LAYER
JP2773050B2 (en) * 1989-08-10 1998-07-09 シーメンス アクチエンゲゼルシヤフト Heat-resistant and corrosion-resistant protective coating layer
US5582635A (en) * 1990-08-10 1996-12-10 Siemens Aktiengesellschaft High temperature-resistant corrosion protection coating for a component in particular a gas turbine component
US5401307A (en) * 1990-08-10 1995-03-28 Siemens Aktiengesellschaft High temperature-resistant corrosion protection coating on a component, in particular a gas turbine component
JP2003147464A (en) 2001-11-02 2003-05-21 Tocalo Co Ltd Member with high-temperature strength
US7754342B2 (en) * 2005-12-19 2010-07-13 General Electric Company Strain tolerant corrosion protecting coating and spray method of application
GB2443283A (en) * 2006-10-26 2008-04-30 Gen Electric Rub coating for gas turbine engine compressors
US7879459B2 (en) * 2007-06-27 2011-02-01 United Technologies Corporation Metallic alloy composition and protective coating
CN102256907B (en) 2008-12-16 2015-07-15 旭硝子株式会社 Filmed metal member for float glass manufacturing equipment and float glass manufacturing method

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Publication number Priority date Publication date Assignee Title
DE102005053531A1 (en) * 2005-11-08 2007-05-10 Man Turbo Ag Heat-insulating protective layer for a component within the hot gas region of a gas turbine

Also Published As

Publication number Publication date
FR2511043B1 (en) 1987-05-22
CA1209827A (en) 1986-08-19
IL66443A (en) 1985-11-29
GB2103656A (en) 1983-02-23
IL66443A0 (en) 1982-12-31
GB2103656B (en) 1985-06-26
FR2511043A1 (en) 1983-02-11
JPS5837146A (en) 1983-03-04
JPH0372706B2 (en) 1991-11-19
DE3229285A1 (en) 1983-03-24

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