EP2330233A1 - A method for making a protective coating on a metal substrate - Google Patents

A method for making a protective coating on a metal substrate Download PDF

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Publication number
EP2330233A1
EP2330233A1 EP09425494A EP09425494A EP2330233A1 EP 2330233 A1 EP2330233 A1 EP 2330233A1 EP 09425494 A EP09425494 A EP 09425494A EP 09425494 A EP09425494 A EP 09425494A EP 2330233 A1 EP2330233 A1 EP 2330233A1
Authority
EP
European Patent Office
Prior art keywords
substrate
nickel
aluminum layer
protective coating
metal substrate
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.)
Withdrawn
Application number
EP09425494A
Other languages
German (de)
French (fr)
Inventor
Ugo Bardi
John Nicholls
Alessandro Lavacchi
Stefano Caporali
Mark Graig
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.)
CONSORZIO INTERUNIVERSITARIO NAZIONALE PER LA SCIE
Cranfield University
Original Assignee
Consorzio Interuniversitario Nazionale per la Scienza Tecnologia dei Materiali
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 Consorzio Interuniversitario Nazionale per la Scienza Tecnologia dei Materiali filed Critical Consorzio Interuniversitario Nazionale per la Scienza Tecnologia dei Materiali
Priority to EP09425494A priority Critical patent/EP2330233A1/en
Publication of EP2330233A1 publication Critical patent/EP2330233A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/30—Manufacture with deposition of material
    • F05D2230/31—Layer deposition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/90—Coating; Surface treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/12—Light metals
    • F05D2300/121—Aluminium

Definitions

  • the present invention relates to a method for making a protective coating on a metal substrate including nickel atoms.
  • This metal substrate is particularly a turbine blade for use in the aeronautic field or in gas plants for producing electric power. At the high operating temperatures of the turbines of this kind, said coating acts as a barrier against substrate oxidation, as well as a "bond coat" for any possible subsequent coating of one or more further protective layers.
  • Said protective layer is known to be obtained by means of rather complicated and expensive methods, particularly the "chemical vapor deposition” (CVD).
  • CVD chemical vapor deposition
  • the object of the present invention is to provide a method as stated in the preamble of the present description, which results in reduced energy consumption and is environment-friendly.
  • this object is achieved by means of a method comprising the steps of
  • the inventive method has the advantages of not requiring high temperatures or the use of dangerous gases and expensive plants, for being implemented.
  • the turbines coated by means of the inventive method has an improved energy performance.
  • This improvement - though poor in absolute terms - is nevertheless very significant in view of the long operating life of a gas turbine.
  • an increase as low as 1 % in the performance of a 50 MW turbine may result in about 1000 tons of gas saved per year, which corresponds to about 200.000 Euro saved per year at present prices.
  • the decrease of fuel consumption further results in the additional advantage of reducing the emission of undesired substances, such as nitrogen and carbon dioxide.
  • the metal substrate being used preferably contains at least 10% by weight of nickel and can be particularly a nickel-based super-alloy, for example one of those that are commercially known as Hastelloy, Inconel, Waspaloy, Rene (e.g. Rene 41, Rene 80, Rene 95, Rene 104), Haynes, Incoloy, MP98T, TMS and the like.
  • nickel-based super-alloy for example one of those that are commercially known as Hastelloy, Inconel, Waspaloy, Rene (e.g. Rene 41, Rene 80, Rene 95, Rene 104), Haynes, Incoloy, MP98T, TMS and the like.
  • the ionic liquid is for example a chloroaluminate of imidazole, pyridinium or ammonium.
  • the electrochemical deposition step is carried out at a temperature ranging between 20 and 50 °C using a current density ranging between 0,5 and 2,5 A/dm 2
  • the vacuum heating step is carried out at a temperature ranging between 900 and 1150 °C and at a pressure ranging between 1 * 10-5 and 133 * 10-5 Pa.
  • the aluminum layer deposited on the substrate can have a thickness ranging between 10 and 100 ⁇ m.
  • a substrate consisting of a nickel alloy made of Ni 72.0%, Cr 15.5%, Fe 8.0%, Si 0.5%, Mn 1.0%, C 0.15%, Cu 0.5%, S ⁇ 0.02% is dipped in a bath of 1-butyl,3-methyl-imidazole hepta-chloroaluminate, made of AIC1 3 and 1-butyl,3-methyl-imidazole chloride at 1:2 molar ratio.
  • an electric current is passed with a density of 1 A/dm 2 .
  • This electrochemical treatment is carried out for 2 hours at ambient temperature thereby causing the formation of a 25 ⁇ m-thick aluminum coating layer on the substrate.
  • the coated substrate is removed from the bath and kept for 2 hours at a temperature of 1120 °C and a pressure of ⁇ 133*10 -5 Pa. Thereby, a coating layer made of the A1 3 Ni and A1Ni compounds is formed by interdiffusion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The method for making a protective coating on a metal substrate including nickel atoms comprises the steps of : electro-chemical deposition of an aluminum layer on the substrate using a bath consisting of a ionic liquid comprising a chloroaluminate anion and an organic cation, and vacuum heating of said substrate on which the aluminum layer has been deposited, such that nickel atoms migrate from the substrate to the aluminum layer, with the formation of a nickel-aluminum alloy-based protective coating.

Description

  • The present invention relates to a method for making a protective coating on a metal substrate including nickel atoms.
  • This metal substrate is particularly a turbine blade for use in the aeronautic field or in gas plants for producing electric power. At the high operating temperatures of the turbines of this kind, said coating acts as a barrier against substrate oxidation, as well as a "bond coat" for any possible subsequent coating of one or more further protective layers.
  • Said protective layer is known to be obtained by means of rather complicated and expensive methods, particularly the "chemical vapor deposition" (CVD).
  • The object of the present invention is to provide a method as stated in the preamble of the present description, which results in reduced energy consumption and is environment-friendly.
  • According to the invention, this object is achieved by means of a method comprising the steps of
    • electro-chemical deposition of an aluminum layer on said substrate using a bath consisting of a ionic liquid comprising a chloroaluminate anion and an organic cation, and
    • vacuum heating of said substrate on which the aluminum layer has been deposited, such that nickel atoms migrate from said substrate to the aluminum layer, with the formation of a nickel-aluminum alloy-based protective coating.
  • The inventive method has the advantages of not requiring high temperatures or the use of dangerous gases and expensive plants, for being implemented.
  • The turbines coated by means of the inventive method has an improved energy performance. This improvement - though poor in absolute terms - is nevertheless very significant in view of the long operating life of a gas turbine. For example, an increase as low as 1 % in the performance of a 50 MW turbine may result in about 1000 tons of gas saved per year, which corresponds to about 200.000 Euro saved per year at present prices. The decrease of fuel consumption further results in the additional advantage of reducing the emission of undesired substances, such as nitrogen and carbon dioxide.
  • The metal substrate being used preferably contains at least 10% by weight of nickel and can be particularly a nickel-based super-alloy, for example one of those that are commercially known as Hastelloy, Inconel, Waspaloy, Rene (e.g. Rene 41, Rene 80, Rene 95, Rene 104), Haynes, Incoloy, MP98T, TMS and the like.
  • The ionic liquid is for example a chloroaluminate of imidazole, pyridinium or ammonium.
  • Advantageously, the electrochemical deposition step is carried out at a temperature ranging between 20 and 50 °C using a current density ranging between 0,5 and 2,5 A/dm2, whereas the vacuum heating step is carried out at a temperature ranging between 900 and 1150 °C and at a pressure ranging between 1 * 10-5 and 133 * 10-5 Pa.
  • Typically, the aluminum layer deposited on the substrate can have a thickness ranging between 10 and 100 µm.
  • An exemplary embodiment of the method according to the invention will be now provided by way of non-limiting illustration.
    • EXAMPLE
  • A substrate consisting of a nickel alloy made of Ni 72.0%, Cr 15.5%, Fe 8.0%, Si 0.5%, Mn 1.0%, C 0.15%, Cu 0.5%, S < 0.02% is dipped in a bath of 1-butyl,3-methyl-imidazole hepta-chloroaluminate, made of AIC13 and 1-butyl,3-methyl-imidazole chloride at 1:2 molar ratio. In the bath, in which an anode made of an AI plate with a purity of more than 99% is provided, an electric current is passed with a density of 1 A/dm2. This electrochemical treatment is carried out for 2 hours at ambient temperature thereby causing the formation of a 25 µm-thick aluminum coating layer on the substrate.
  • Subsequently, the coated substrate is removed from the bath and kept for 2 hours at a temperature of 1120 °C and a pressure of < 133*10-5 Pa. Thereby, a coating layer made of the A13Ni and A1Ni compounds is formed by interdiffusion.
  • Obviously, the principle of the invention being understood, the implementation details and the embodiments thereof may be widely changed relative to what has been described herein by way of example, without however departing from the scope of the invention as defined in the annexed claims.

Claims (8)

  1. A method for making a protective coating on a metal substrate including nickel atoms, comprising the steps of
    - electro-chemical deposition of an aluminum layer on said substrate using a ionic liquid bath comprising a chloroaluminate anion and an organic cation, and
    - vacuum heating of said substrate on which the aluminum layer has been deposited, such that nickel atoms migrate from said substrate to the aluminum layer, with the formation of a nickel-aluminum alloy-based protective coating.
  2. The method according to claim 1, wherein said step of electrochemical deposition is carried out at a temperature ranging between 20 and 50 °C.
  3. The method according to any preceding claim, wherein said step of electrochemical deposition provides for the use of a current density ranging between 0.5 and 2.5 A/dm2.
  4. The method according to any preceding claim, wherein said step of vacuum heating is carried out at a temperature ranging between 900 and 1150 °C and at a pressure ranging between 1 * 10-5 and 133 * 10-5 Pa.
  5. The method according to any preceding claim, wherein said metal substrate contains at least 10% nickel by weight.
  6. The method according to any preceding claim, wherein said metal substrate is a nickel-based super-alloy.
  7. The method according to any preceding claim, wherein said ionic liquid is a chloroaluminate of imidazole, pyridinium or ammonium.
  8. The method according to any preceding claim, wherein said aluminum layer has a thickness ranging between 10 and 100 µm.
EP09425494A 2009-12-01 2009-12-01 A method for making a protective coating on a metal substrate Withdrawn EP2330233A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09425494A EP2330233A1 (en) 2009-12-01 2009-12-01 A method for making a protective coating on a metal substrate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09425494A EP2330233A1 (en) 2009-12-01 2009-12-01 A method for making a protective coating on a metal substrate

Publications (1)

Publication Number Publication Date
EP2330233A1 true EP2330233A1 (en) 2011-06-08

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Country Status (1)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8778164B2 (en) 2010-12-16 2014-07-15 Honeywell International Inc. Methods for producing a high temperature oxidation resistant coating on superalloy substrates and the coated superalloy substrates thereby produced
WO2014130452A1 (en) * 2013-02-19 2014-08-28 Alumiplate, Inc. Hard aluminum films formed using high current density plating
EP2450477A3 (en) * 2010-11-05 2015-08-12 United Technologies Corporation Coating method for reactive metal
EP2966190A4 (en) * 2013-03-07 2017-01-25 Hitachi, Ltd. Method for forming aluminide coating film on base
US9771661B2 (en) 2012-02-06 2017-09-26 Honeywell International Inc. Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates
US10087540B2 (en) 2015-02-17 2018-10-02 Honeywell International Inc. Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1995344A1 (en) * 2007-05-25 2008-11-26 InnCoa GmbH Injection layers with diffusion treatment

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1995344A1 (en) * 2007-05-25 2008-11-26 InnCoa GmbH Injection layers with diffusion treatment

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ANDREW P. ABBOTT AND KATY J. MCKENZIE: "Application of ionic liquids to the electrodeposition of metals", PHYS. CHEM. CHEM. PHYS, no. 8, 28 July 2006 (2006-07-28), pages 4265 - 4279, XP002577503, DOI: 10.1039/b607329h *
I.USOV, P.ARENDT, L.STAN, R.DE PAULA, H.WANG, S.FOLTYN AND P.DOWDEN: "Characteristics of alumina diffusion barrier films on Hastelloy", J.MATER. RES., vol. 19, no. 4, April 2004 (2004-04-01), pages 1175 - 1180, XP002577502 *
T.TSUDA, C.L.HUSSEY AND G.R.STAFFORD: "Progress in Surface Finishing with Lewis Acidic Room-Temperature Chloroaluminate Ionic liquids", MEET.ABSTR. ELECTROCHEM. SOC., no. 602, 2037, 2006, XP002577504, ISSN: 1091-8213 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2450477A3 (en) * 2010-11-05 2015-08-12 United Technologies Corporation Coating method for reactive metal
US8778164B2 (en) 2010-12-16 2014-07-15 Honeywell International Inc. Methods for producing a high temperature oxidation resistant coating on superalloy substrates and the coated superalloy substrates thereby produced
US9771661B2 (en) 2012-02-06 2017-09-26 Honeywell International Inc. Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates
WO2014130452A1 (en) * 2013-02-19 2014-08-28 Alumiplate, Inc. Hard aluminum films formed using high current density plating
US10000859B2 (en) 2013-02-19 2018-06-19 Alumiplate, Inc. Hard aluminum films formed using high current density plating
EP2966190A4 (en) * 2013-03-07 2017-01-25 Hitachi, Ltd. Method for forming aluminide coating film on base
US10087540B2 (en) 2015-02-17 2018-10-02 Honeywell International Inc. Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same

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