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 PDFInfo
- 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- Withdrawn
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 8
- 239000002184 metal Substances 0.000 title claims abstract description 8
- 239000011253 protective coating Substances 0.000 title claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002608 ionic liquid Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000002892 organic cations Chemical class 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 229910000601 superalloy Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910001293 incoloy Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001088 rené 41 Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001247 waspaloy Inorganic materials 0.000 description 1
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.
- 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)
- 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.
- The method according to claim 1, wherein said step of electrochemical deposition is carried out at a temperature ranging between 20 and 50 °C.
- 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.
- 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.
- The method according to any preceding claim, wherein said metal substrate contains at least 10% nickel by weight.
- The method according to any preceding claim, wherein said metal substrate is a nickel-based super-alloy.
- The method according to any preceding claim, wherein said ionic liquid is a chloroaluminate of imidazole, pyridinium or ammonium.
- The method according to any preceding claim, wherein said aluminum layer has a thickness ranging between 10 and 100 µm.
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 |
Family
ID=42061111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09425494A Withdrawn EP2330233A1 (en) | 2009-12-01 | 2009-12-01 | A method for making a protective coating on a metal substrate |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP2330233A1 (en) |
Cited By (6)
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1995344A1 (en) * | 2007-05-25 | 2008-11-26 | InnCoa GmbH | Injection layers with diffusion treatment |
-
2009
- 2009-12-01 EP EP09425494A patent/EP2330233A1/en not_active Withdrawn
Patent Citations (1)
| 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)
| 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)
| 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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| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: GRAIG, MARK Inventor name: CAPORALI, STEFANO Inventor name: LAVACCHI, ALESSANDRO Inventor name: NICHOLLS, JOHN Inventor name: BARDI, UGO |
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