EP3608450A2 - Procédé pour fourniture d'une surface métallique dotée d'une couche protectrice contre la diffusion de chrome - Google Patents

Procédé pour fourniture d'une surface métallique dotée d'une couche protectrice contre la diffusion de chrome Download PDF

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Publication number
EP3608450A2
EP3608450A2 EP19189589.5A EP19189589A EP3608450A2 EP 3608450 A2 EP3608450 A2 EP 3608450A2 EP 19189589 A EP19189589 A EP 19189589A EP 3608450 A2 EP3608450 A2 EP 3608450A2
Authority
EP
European Patent Office
Prior art keywords
slip
equal
range
less
powder
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Withdrawn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
EP19189589.5A
Other languages
German (de)
English (en)
Other versions
EP3608450A3 (fr
Inventor
Heinrich Walter
Ludwig Hilser
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.)
MTU Aero Engines AG
Original Assignee
MTU Aero Engines AG
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 MTU Aero Engines AG filed Critical MTU Aero Engines AG
Publication of EP3608450A2 publication Critical patent/EP3608450A2/fr
Publication of EP3608450A3 publication Critical patent/EP3608450A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • C23C10/32—Chromising
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • 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
    • F05D2220/00—Application
    • F05D2220/30—Application in turbines
    • F05D2220/32—Application in turbines in gas turbines
    • 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
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
    • F05D2300/132—Chromium
    • 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
    • F05D2300/20—Oxide or non-oxide ceramics
    • F05D2300/22—Non-oxide ceramics
    • F05D2300/222—Silicon
    • 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
    • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
    • F05D2300/611—Coating
    • 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
    • F05D2300/70—Treatment or modification of materials
    • F05D2300/701—Heat treatment

Definitions

  • the present invention relates to a method for coating a metallic surface, for example a surface of a component of a turbomachine, with a diffusion protection layer made from a chromium-containing slip, and in particular to a method which shortens the holding time during the heat treatment of the coated component to produce a Chrome diffusion protection layer on the metallic surface enables.
  • components such as Turbine blades made of, for example, nickel-based superalloys for protection against oxidation and corrosion at the high temperatures prevailing during operation of the gas turbines are usually provided with a diffusion protective layer.
  • a chromium-containing slip for example, is usually applied to the component in several layers, whereupon the component coated in this way is heated to high temperatures (for example 800 ° C. to 1250 ° C.), so that the chromium diffuses in the slip effect in the surface of the component and thereby improve the oxidation and corrosion resistance of the surface.
  • the production of the chrome diffusion protection layer can be followed by an alitation (e.g.
  • a metallic surface coated according to the method according to the invention is also the subject of the present invention, as is a slip suitable for the method according to the invention.
  • a metallic surface for example a surface of a component of a turbomachine
  • a chromium diffusion protection layer one or more layers (for example at least two layers or layers) of a chromium-containing slip are applied to the surface to be coated, wherein before the application of a layer to an already applied layer, the already applied layer is preferably dried.
  • the slip used also contains silicon powder. Surprisingly, it was found that this accelerates the diffusion of the chromium into the metallic surface and thus the required holding time of the component at the required high temperatures can be shortened.
  • the weight ratio of chrome powder to silicon powder in the slip is in most cases at least 5: 1, e.g. at least 6: 1, at least 7: 1, at least 8: 1, at least 9: 1, at least 9.5: 1 or at least 10: 1, and is usually not higher than 100: 1, e.g. not higher than 75: 1, not higher than 50: 1, not higher than 40: 1, or not higher than 30: 1.
  • Both the chrome powder and the silicon powder generally have a maximum grain size and / or an average grain size of less than or equal to 20 ⁇ m, in particular less than or equal to 10 ⁇ m, preferably less than or equal to 5 ⁇ m.
  • the slip is applied at room temperature (20-25 ° C).
  • the temperature of the surface to be coated can also be significantly higher, but preferably not higher than 200 ° C.
  • the resulting layer is preferably dried before (optionally) a further layer is applied. Drying is preferably carried out at elevated temperature, for example in the range from 50 ° C. to 200 ° C., for example in the range from 80 ° C. to 150 ° C.
  • the drying can take place in an air atmosphere or in a vacuum or in a protective gas atmosphere (eg argon atmosphere).
  • Two, three, four, five, six, seven, eight, nine, ten or more layers of slip can be applied in succession.
  • the thickness of a layer that has not yet dried is often in the range from 1 ⁇ m to 60 ⁇ m.
  • the thickness of the layer is reduced by drying, the extent of the reduction depending inter alia on the solids content of the slip used.
  • the thickness of the finished coating (after application and drying of all layers) is usually in the range from 40 ⁇ m to 10 mm, in particular in the range from 50 ⁇ m to 5 mm, for example in the range from 60 ⁇ m to 2 mm.
  • a slip suitable for the method according to the invention contains at least three essential constituents, namely particulate chromium, particulate silicon and binder.
  • the slip usually also contains water and / or one or more organic solvents.
  • the slip can also contain one or more further constituents, for example metal halide (for example CrCl 3 ) and / or inert substance particles (for example Al 2 O 3 ).
  • binders are suitable as binders, in particular organic polymers (resins).
  • organic polymers include epoxy resins, silicones, alkyd resins, acrylic resins, polyurethanes, polyvinyl chloride, polyvinyl alcohol, phenolic resins, polyesters, polyamides and polyolefins.
  • suitable organic solvents are all those used in the paint industry.
  • Nonlimiting specific examples include alcohols such as methanol, ethanol, isopropanol and butanol; Glycols and glycol-containing compounds such as ethylene glycol and ethylene glycol alkyl ether; Ethers, esters, amines, amides, ketones, aldehydes, aromatic compounds such as toluene and xylene; and chlorinated hydrocarbons.
  • the slip used according to the invention can comprise water and / or at least one liquid organic compound, in particular an oil, preferably screen printing oil.
  • the slip can be applied to the metallic surface in any manner, for example using techniques known in the paint industry, such as spraying, brushing, dipping, pouring, roller coating and spin coating.
  • the metallic surface to be coated can consist, for example, of a pure metal and / or an alloy.
  • alloys include those which are used in the production of components of turbomachines, in particular so-called super alloys based on nickel and / or cobalt and / or iron, which contain one or more additional metals, such as, for example, Re, W. , Mo, Nb, Ta, and Ti.
  • Non-limiting examples of metal substrates that can be coated with the method according to the invention include components of turbomachines (in particular gas turbines), for example, blades of guide blades and moving blades, blade cover bands, blade platforms and parts thereof.
  • turbomachines in particular gas turbines
  • blades of guide blades and moving blades for example, blades of guide blades and moving blades, blade cover bands, blade platforms and parts thereof.
  • the coated substrate is heated in a vacuum and / or under a protective gas atmosphere (for example argon) to a temperature which enables the chromium in the layer or layers to diffuse the coated metallic surface into it.
  • a protective gas atmosphere for example argon
  • the temperature required for this depends on various factors, including the composition of the metallic surface, the desired depth of penetration into the surface, the composition of the slip, and the thickness of the slip layer (s). In most cases, this temperature is in the range from 800 ° C. to 1250 ° C., in particular in the range from 900 ° C. to 1200 ° C. and preferably in the range from 1000 ° C. to 1150 ° C.
  • the required holding times at these temperatures are generally in the range from 1 h to 24 h, in particular from 2 h to 12 h, preferably from 3 h to 6 h. Due to the presence of silicon in the slip the required holding time is shortened (the diffusion of chromium into the metallic surface is accelerated), for example by at least 5%, at least 10%, at least 15%, at least 20% or at least 25% of the required holding time in the absence of silicon.
  • the heat treatment for producing a diffusion protection layer is also preferably carried out in an atmosphere which contains one or more chromium halides, in particular a chromium chloride, preferably CrCl 2 .
  • An alitation preferably follows the production of the chromium diffusion protection layer.
  • the alitation can be carried out, for example, as gas phase alitation, in which aluminum-containing donor material, such as aluminum powder, together with an activator or a starting material for an activator, such as a halogen compound, is exposed to a high temperature for a certain time in order to enrich aluminum to effect the surface of the component treated accordingly.
  • a reducing atmosphere for example of a 3/8 mixture of a protective gas or inert gas, such as argon, and hydrogen can be provided in the corresponding reaction chamber.
  • a component made of the PW 1484 alloy which contains approximately 5% by weight of chromium, approximately 2% by weight of molybdenum, approximately 6% of tungsten, approximately 3% by weight of rhenium, approximately 9% by weight of tantalum, approximately 5% by weight.
  • the slip was applied to the component to be coated by spraying. After the application, the slip was dried at 50 ° C. in vacuo and then at 100 ° C. in air for up to half an hour. The thickness of the slip thus dried was 150 ⁇ m. Thereafter, the component was subjected to a heat treatment at a temperature of 1080 ° C in an argon atmosphere containing a small amount of CrCl 2 for 4 hours.
  • FIG. 1 shows a section (after molybdic acid etching) of a coated surface produced in this way (magnification 1000: 1).
  • the diffusion protection layer 2 produced on the component 1 was approximately 20 ⁇ m thick.
  • An analysis of the surface of the component showed the concentrations of the elements present therein (in% by weight) as a function of the distance from the outer surface of the diffusion protection layer 2, as shown in the following table.
  • both chromium and silicon had diffused into component 1 up to a distance of approximately 20 ⁇ m from the surface.
  • the coated component was then subjected to a gas phase alitation, in which the aluminum-containing donor material was deposited on the component using the activator AIF 3 .
  • the alitation was carried out at a temperature of approximately 1100 ° C. for 6 h in an argon-hydrogen atmosphere.
  • FIG. 2 shows a section (after molybdic acid etching) of the alitated coated surface (magnification 500: 1). How from FIG. 2 can be seen, was by the alitation on the approximately 20 microns thick chrome diffusion protection layer 2, which in FIG. 1 is shown, an approx. 60 ⁇ m thick alitation layer 3 is formed, which mainly consisted of aluminum.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
EP19189589.5A 2018-08-09 2019-08-01 Procédé pour fourniture d'une surface métallique dotée d'une couche protectrice contre la diffusion de chrome Withdrawn EP3608450A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102018213395.6A DE102018213395A1 (de) 2018-08-09 2018-08-09 Verfahren zum versehen einer metallischen oberfläche mit einer chrom-diffusionsschutzschicht

Publications (2)

Publication Number Publication Date
EP3608450A2 true EP3608450A2 (fr) 2020-02-12
EP3608450A3 EP3608450A3 (fr) 2020-04-08

Family

ID=67658376

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19189589.5A Withdrawn EP3608450A3 (fr) 2018-08-09 2019-08-01 Procédé pour fourniture d'une surface métallique dotée d'une couche protectrice contre la diffusion de chrome

Country Status (3)

Country Link
US (1) US20200048755A1 (fr)
EP (1) EP3608450A3 (fr)
DE (1) DE102018213395A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128179A (en) * 1981-07-08 1992-07-07 Alloy Surfaces Company, Inc. Metal diffusion and after-treatment
GB2378452A (en) * 2001-08-09 2003-02-12 Rolls Royce Plc A metallic article having a protective coating and a method therefor
US8262812B2 (en) * 2007-04-04 2012-09-11 General Electric Company Process for forming a chromium diffusion portion and articles made therefrom
EP2695964B1 (fr) * 2012-08-10 2020-05-06 MTU Aero Engines AG Couche de protection adaptée au composant
DE102014222024A1 (de) * 2014-10-29 2016-06-16 MTU Aero Engines AG Schlicker und Verfahren zur Herstellung einer Oxidations- und Korrosionsbeständigen Diffusionschicht

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Publication number Publication date
DE102018213395A1 (de) 2020-02-13
US20200048755A1 (en) 2020-02-13
EP3608450A3 (fr) 2020-04-08

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