EP0241807B1 - Revêtement résistant à haute température - Google Patents

Revêtement résistant à haute température Download PDF

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Publication number
EP0241807B1
EP0241807B1 EP87104785A EP87104785A EP0241807B1 EP 0241807 B1 EP0241807 B1 EP 0241807B1 EP 87104785 A EP87104785 A EP 87104785A EP 87104785 A EP87104785 A EP 87104785A EP 0241807 B1 EP0241807 B1 EP 0241807B1
Authority
EP
European Patent Office
Prior art keywords
weight
alloy
chromium
nickel
cobalt
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 - Lifetime
Application number
EP87104785A
Other languages
German (de)
English (en)
Other versions
EP0241807A2 (fr
EP0241807A3 (en
Inventor
Lorenz Dr. Dr.-Ing. Singheiser
Georg Dr. Dipl.-Phys. Wahl
Bernd Dr. Dipl.-Phys. Jahnke
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.)
ASEA BROWN BOVERI AKTIENGESELLSCHAFT
Original Assignee
Asea Brown Boveri AG Germany
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 Asea Brown Boveri AG Germany filed Critical Asea Brown Boveri AG Germany
Publication of EP0241807A2 publication Critical patent/EP0241807A2/fr
Publication of EP0241807A3 publication Critical patent/EP0241807A3/de
Application granted granted Critical
Publication of EP0241807B1 publication Critical patent/EP0241807B1/fr
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Classifications

    • 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
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component

Definitions

  • the invention relates to a high-temperature protective layer according to the preamble of claims 1, 2 and 3.
  • Such high-temperature protective layers are used above all where the base material of components made of heat-resistant steels and / or alloys that are used at temperatures above 600 ° C is to be protected.
  • high-temperature protective layers are intended to slow down or completely prevent the effects of high-temperature corrosion, especially of sulfur, oil ash, oxygen, alkaline earths and vandium.
  • Such high-temperature protective layers are designed so that they can be applied directly to the base material of the component to be protected.
  • High-temperature protective layers are of particular importance for components of gas turbines. They are mainly applied to rotor blades and guide vanes as well as to heat accumulation segments in gas turbines.
  • An austenitic material based on nickel, cobalt or iron is preferably used to manufacture these components.
  • nickel superalloys in particular are used as the base material.
  • Components that are intended for gas turbines are provided with protective layers that are formed by an alloy that contains nickel, cobalt, chromium, aluminum and yttrium.
  • the aluminum content of these alloys is relatively high, while the chromium content is quite low, which leads to poor corrosion resistance. This is solely due to the low chromium content.
  • Protective layers which are made from the abovementioned alloys have the property that, under operating conditions, in particular when they are exposed to a temperature of more than 900 °, they form an aluminum oxide-containing cover layer on their surface.
  • the yttrium contained in the alloy results in a certain adhesive strength of the aluminum oxide cover layer on the protective layer.
  • the structure of these protective layers consists of a matrix in which an aluminum-containing phase is embedded. Progressive oxidation leads to a rapid depletion of aluminum near the surface. This leads to an increased susceptibility of the protective layers to corrosion.
  • a protective layer is known from FR-A-2 551 043, which contains cobalt, chromium, aluminum, silicon, yttrium and nickel.
  • the oxidation and corrosion resistance of this protective layer is inadequate, which is caused by the special composition of the alloy, especially the low chromium content.
  • a cobalt-based protective layer is known from US-A-4,034,142. In addition to cobalt, it contains chrome, aluminum, nickel, yttrium and silicon. However, the present patent application is aimed at the formation of a protective layer based on nickel.
  • FR-A-2 205 578 describes two further protective layers based on nickel. However, the chromium content of these layers is too low to ensure a sufficiently high resistance to oxidation and corrosion.
  • EP-A-134 821 Another protective layer is described in EP-A-134 821, which also contains chromium, aluminum, nickel, silicon, zirconium and tantalum. However, the oxidation and corrosion resistance of this layer does not meet the necessary requirements.
  • the invention has for its object to show a high-temperature protective layer which has a low oxidation rate, is corrosion-resistant, and is additionally adapted to the base materials of the components even at high temperatures.
  • the adhesive strength of the metallic oxide layer that forms, in particular the aluminum oxide cover layer that is formed is increased by adding silicon, and the corrosion resistance of the high-temperature protective layer is thereby significantly increased.
  • Adding zirconium and silicon to such an alloy increases the resistance to oxidation and corrosion, and the chromium content can be kept very high.
  • the amount of zirconium added to the alloy according to claim 3 is 1% by weight based on the total weight of the alloy.
  • the low solubility of zirconium in an alloy based on nickel leads to the elimination of zirconium-rich phases.
  • Such an alloy can be used according to claim 1 or 2 with a very small amount of yttrium, for example 0.1 to 1% by weight based on the total weight of the alloy or without yttrium.
  • tantalum according to claim 1 increases its oxidation resistance, improves the adhesion of the oxide layer and thereby increases the corrosion resistance.
  • the tantalum added to the alloy is present in solution in the matrix. 1% by weight of tantalum is added to the alloy.
  • Corrosion-resistant protective layers are, however, achieved particularly well if silicon is added to the alloy in addition to the tantalum.
  • small additions of titanium can be added to the alloy. However, the amount should only be between 0.1 and 2% by weight based on the total weight of the alloy.
  • the additions of silicon, silicon and zirconium or silicon and tantalum enable the alloy to have a very large chromium, aluminum and cobalt content.
  • the chromium content can be between 18 and 27% by weight, the cobalt content 3 up to 20% by weight and the aluminum content 7 up to 12% by weight, based on the total weight of the alloy.
  • the amounts of chromium, aluminum and cobalt can also be selected to be lower. This enables a very good adaptation to the nickel-containing base material of the components. The same also applies to oxide dispersion hardened alloys, from which many components to be protected are also made.
  • the protective layer is compatible with these alloys even at very high temperatures.
  • a particularly advantageous high-temperature protective layer which has very good resistance to oxidation and corrosion, is formed by an alloy which contains 18 to 25% by weight of chromium, 7 to 12% by weight of aluminum, 0.5 to 3% by weight of silicon, 0 , 5 to 1 wt.% Yttrium and 3 to 15 wt.% Cobalt, and the rest of which consists of nickel.
  • This alloy can have additions of titanium in amounts of between 0.1 and 2% by weight.
  • the above weight data refer to the total weight of the alloy.
  • An alloy modified with tantalum by which the adhesive strength of the self-forming aluminum oxide top layer is particularly favored, preferably contains 18 to 25% by weight of chromium, 7 to 12% by weight of aluminum, 0.5 to 3% by weight of silicon, 0.5 up to 1 wt% yttrium, 1 wt% tantalum, 3 to 15 wt% cobalt.
  • the rest of the alloy is nickel. This alloy also permits the addition of titanium in amounts between 0.1 and 2% by weight, should this addition be necessary.
  • composition of an alloy for forming the high-temperature protective layer in which the yttrium can optionally be dispensed with, preferably has 18 to 27% by weight of chromium, 8 to 12% by weight of aluminum, 0.5 to 3% by weight of silicon, 1% by weight, zirconium, 5 to 20% by weight of cobalt and a proportion of nickel which forms the remaining constituent of the alloy. All weight data in the alloy compositions shown above relate to the respective total weight of the alloy.
  • a high-temperature protective layer which is formed from this alloy, has a chromium-rich, low-aluminum matrix with a high volume fraction of an aluminum-rich phase, as well as further precipitations with a high zirconium and silicon content.
  • All of the alloys described here are suitable for the formation of a high-temperature protective layer. Regardless of which of the alloys described above they are formed, an aluminum oxide cover layer is formed in each case under operating conditions on these protective layers, which are not removed even at temperatures that are greater than 900 ° C.
  • the gas turbine component to be coated is made of an austenitic material, in particular a nickel superalloy.
  • the component is first chemically cleaned and then roughened with a sandblast.
  • the component is coated under vacuum using the plasma spraying process.
  • An alloy is used for the coating, which contains 18 to 25 wt.% Chromium, 7 to 12 wt.% Aluminum, 0.5 to 3 wt.% Silicon, 0.5 to 1 wt.% Yttrium and 3 to 15 wt. % Has cobalt.
  • the rest of the alloy consists of nickel.
  • an alloy which contains 18 to 27% by weight of chromium, 8 to 12% by weight of aluminum, 0.5 to 3% by weight of silicon, 1% by weight of zirconium and 5 to 20% by weight of cobalt has, the remaining portion of the alloy is nickel.
  • the plasma spraying process can also be used to apply an alloy which contains 18 to 25% by weight of chromium, 7 to 12% by weight of aluminum, 0.5 to 3% by weight of silicon, 0.5 to 1% by weight of yttrium, 1% by weight. % Tantalum and 3 to 15% by weight cobalt has, the remaining portion of the alloy consists of nickel.
  • the material forming the alloy is in powder form and preferably has a grain size of 45 ⁇ m.
  • the component is heated to 800 ° C. using the plasma.
  • the alloy is applied directly to the base material of the component. Argon and hydrogen are used as the plasma gas.
  • the component is subjected to a heat treatment. This takes place in a high vacuum annealing furnace. A pressure of less than 5x10 ⁇ 3 Torr is maintained in it. After reaching the vacuum, the furnace is heated to a temperature of 1100 ° C. The above temperature is held for about 1 hour with a tolerance of about +/- 4 ° C. The heating of the furnace is then switched off. The coated and heat-treated component is slowly cooled in the oven. Its production is finished after cooling.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (3)

  1. Couche de protection contre les hautes températures consistant en un alliage contenant du nickel, du cobalt, du chrome, de l'aluminium et de l'yttrium, en particulier pour des éléments de construction consistant en une matière austénitique, caractérisée en ce que l'alliage contient 18 à 25 % en poids de chrome, 7 à 12 % en poids d'aluminium 0,5 à 3 % en poids de silicium, 0,5 à 1 % en poids d'yttrium, 1 % en poids de tantale et 3 à 15 % en poids de cobalt, par rapport à son poids total, le reste de l'alliage consistant en nickel.
  2. Couche de protection contre les hautes températures consistant en un alliage contenant du nickel, du cobalt, du chrome, de l'aluminium et de l'yttrium, en particulier pour des éléments de construction consistant en une matière austénitique, caractérisée en ce que l'alliage contient 18 à 25 % en poids de chrome, 7 à 12 % en poids d'aluminium, 0,5 à 3 % en poids de silicium, 0,5 à 1 % en poids d'yttrium et 3 à 15 % en poids de cobalt, par rapport à son poids total, le reste de l'alliage consistant en nickel.
  3. Couche de protection contre les hautes températures consistant à un alliage contenant du nickel, du cobalt, du chrome et de l'aluminium, en particulier pour des éléments de construction consistant en une matière austénitique, caractérisée en ce que l'alliage contient 18 à 27 % en poids de chrome, 8 à 12 % en poids d'aluminium, 0,5 à 3 % en poids de silicium, 1 % en poids de zirconium et 5 à 20 % en poids de cobalt, par rapport à son poids total, le reste de l'alliage consistant en nickel.
EP87104785A 1986-04-15 1987-04-01 Revêtement résistant à haute température Expired - Lifetime EP0241807B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863612568 DE3612568A1 (de) 1986-04-15 1986-04-15 Hochtemperatur-schutzschicht
DE3612568 1986-04-15

Publications (3)

Publication Number Publication Date
EP0241807A2 EP0241807A2 (fr) 1987-10-21
EP0241807A3 EP0241807A3 (en) 1988-02-24
EP0241807B1 true EP0241807B1 (fr) 1991-07-24

Family

ID=6298672

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87104785A Expired - Lifetime EP0241807B1 (fr) 1986-04-15 1987-04-01 Revêtement résistant à haute température

Country Status (4)

Country Link
US (1) US4909984A (fr)
EP (1) EP0241807B1 (fr)
JP (1) JP2574287B2 (fr)
DE (2) DE3612568A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013209189A1 (de) * 2013-05-17 2014-11-20 Siemens Aktiengesellschaft Schutzbeschichtung und Gasturbinenkomponente mit der Schutzbeschichtung
US11092034B2 (en) * 2011-08-09 2021-08-17 Siemens Energy Global Gmbh & Co, Kg Alloy, protective layer and component

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3737361A1 (de) * 1987-11-04 1989-05-24 Deutsche Forsch Luft Raumfahrt Nickel enthaltende legierungen, verfahren zu ihrer herstellung und ihre verwendung
DE3740478C1 (de) * 1987-11-28 1989-01-19 Asea Brown Boveri Hochtemperatur-Schutzschicht
US5002834A (en) * 1988-04-01 1991-03-26 Inco Alloys International, Inc. Oxidation resistant alloy
DE3842301A1 (de) * 1988-12-16 1990-06-21 Asea Brown Boveri Hochtemperatur-schutzschicht
DE3842300A1 (de) * 1988-12-16 1990-06-21 Asea Brown Boveri Hochtemperatur-schutzschicht
US6737556B2 (en) * 2002-10-21 2004-05-18 Exxonmobil Chemical Patents Inc. Method and system for reducing decomposition byproducts in a methanol to olefin reactor system
DE112004000275T5 (de) * 2003-02-11 2006-03-16 The Nanosteel Co., Maitland Hochaktive flüssige Schmelzen zur Bildung von Beschichtungen
US7951459B2 (en) * 2006-11-21 2011-05-31 United Technologies Corporation Oxidation resistant coatings, processes for coating articles, and their coated articles
US8354176B2 (en) * 2009-05-22 2013-01-15 United Technologies Corporation Oxidation-corrosion resistant coating
TW201133517A (en) * 2010-03-23 2011-10-01 Yageo Corp Chip resistor having a low resistance and method for manufacturing the same
CN102717553A (zh) * 2012-06-29 2012-10-10 苏州嘉言能源设备有限公司 槽式太阳能集热器用耐蚀涂层
CN102719825A (zh) * 2012-06-29 2012-10-10 苏州嘉言能源设备有限公司 太阳能热发电耐腐蚀保护涂层
US10308818B2 (en) * 2016-05-19 2019-06-04 United Technologies Corporation Article having coating with glass, oxygen scavenger, and metal
DE102020213918A1 (de) 2020-11-05 2022-05-05 Siemens Energy Global GmbH & Co. KG Legierung, Pulver, duktile gamma`-Haftvermittlerschicht und Bauteil

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0134821A1 (fr) * 1983-07-22 1985-03-27 BBC Aktiengesellschaft Brown, Boveri & Cie. Revêtement protecteur à haute température

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GB583807A (en) * 1943-06-30 1946-12-31 Harold Ernest Gresham Nickel base alloy
GB1426438A (en) * 1972-11-08 1976-02-25 Rolls Royce Nickel or cobalt based alloy composition
GB1512811A (en) * 1974-02-28 1978-06-01 Brunswick Corp Abradable seal material and composition thereof
US4034142A (en) * 1975-12-31 1977-07-05 United Technologies Corporation Superalloy base having a coating containing silicon for corrosion/oxidation protection
SE408161B (sv) * 1978-04-05 1979-05-21 Tetra Pak Int Anordning for sterilisering av en forpackningsmaterialbana
US4339509A (en) * 1979-05-29 1982-07-13 Howmet Turbine Components Corporation Superalloy coating composition with oxidation and/or sulfidation resistance
DE3064929D1 (en) * 1979-07-25 1983-10-27 Secr Defence Brit Nickel and/or cobalt base alloys for gas turbine engine components
US4312682A (en) * 1979-12-21 1982-01-26 Cabot Corporation Method of heat treating nickel-base alloys for use as ceramic kiln hardware and product
US4326011A (en) * 1980-02-11 1982-04-20 United Technologies Corporation Hot corrosion resistant coatings
US4447503A (en) * 1980-05-01 1984-05-08 Howmet Turbine Components Corporation Superalloy coating composition with high temperature oxidation resistance
US4419416A (en) * 1981-08-05 1983-12-06 United Technologies Corporation Overlay coatings for superalloys
CA1209827A (fr) * 1981-08-05 1986-08-19 David S. Duvall Enduits de surcouche a forte teneur d'yttrium
US4439248A (en) * 1982-02-02 1984-03-27 Cabot Corporation Method of heat treating NICRALY alloys for use as ceramic kiln and furnace hardware
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EP0207874B1 (fr) * 1985-05-09 1991-12-27 United Technologies Corporation Revêtements protecteurs pour superalliages, bien adaptés aux substrats

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0134821A1 (fr) * 1983-07-22 1985-03-27 BBC Aktiengesellschaft Brown, Boveri & Cie. Revêtement protecteur à haute température

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11092034B2 (en) * 2011-08-09 2021-08-17 Siemens Energy Global Gmbh & Co, Kg Alloy, protective layer and component
DE102013209189A1 (de) * 2013-05-17 2014-11-20 Siemens Aktiengesellschaft Schutzbeschichtung und Gasturbinenkomponente mit der Schutzbeschichtung

Also Published As

Publication number Publication date
EP0241807A2 (fr) 1987-10-21
EP0241807A3 (en) 1988-02-24
JP2574287B2 (ja) 1997-01-22
DE3612568A1 (de) 1987-10-29
DE3771546D1 (de) 1991-08-29
JPS62250142A (ja) 1987-10-31
US4909984A (en) 1990-03-20

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