EP2695965A2 - Revêtement CrAl à phases duplex pour une meilleure protection contre la corrosion/l'oxydation - Google Patents

Revêtement CrAl à phases duplex pour une meilleure protection contre la corrosion/l'oxydation Download PDF

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Publication number
EP2695965A2
EP2695965A2 EP13178306.0A EP13178306A EP2695965A2 EP 2695965 A2 EP2695965 A2 EP 2695965A2 EP 13178306 A EP13178306 A EP 13178306A EP 2695965 A2 EP2695965 A2 EP 2695965A2
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EP
European Patent Office
Prior art keywords
chromium
weight
coating
aluminum
equal
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Withdrawn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
EP13178306.0A
Other languages
German (de)
English (en)
Other versions
EP2695965A3 (fr
Inventor
Horst Pillhöfer
Stefan Müller
Erwin Bayer
Thomas Dautl
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
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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 EP2695965A2 publication Critical patent/EP2695965A2/fr
Publication of EP2695965A3 publication Critical patent/EP2695965A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • 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
    • C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/60—After-treatment
    • 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.]
    • Y10T428/12639—Adjacent, identical composition, components

Definitions

  • the present invention relates to a coating for components which are exposed to high temperatures and aggressive media, such as components of gas turbines and in particular aircraft engines. Moreover, the present invention relates to a method for producing such coatings as well as correspondingly produced components.
  • corrosion and / or high-temperature oxidation protective layers which may also contain chromium and / or aluminum.
  • corresponding protective layers must also have mechanical properties which avoid damage or destruction of the protective layers under the given conditions of use, since mechanical damage to the layers can again lead to an increased corrosion attack or oxidation attack.
  • various coatings are known in the art, which have chromium and / or aluminum.
  • An example is in the WO 2006/026456 given in which chromium layers with 30% chromium portion are described, which additionally have aluminum.
  • Another example is in the DE 10 2008 039 969 A1 described that discloses chromium layers with more than 30 wt .-% chromium content.
  • aircraft are operated above the sea or near the sea, so that saline air and, correspondingly, salt particles can be introduced into the engines.
  • the fuel may contain other elements, such as sulfur, sodium, calcium and potassium, which can cause corrosion.
  • the engines also have high operating temperatures during operation, there are also severe high-temperature oxidation conditions. Consequently, corresponding components, such as turbine blades in the low-pressure turbine of an aircraft engine, must both withstand high temperatures and be protected against corrosion, such as sulfidation.
  • the previous coatings do not provide a satisfactory result here.
  • a method for the corresponding coating of components is to be specified, which is easy to carry out and allows a reliable coating that offers such high-stress components high-temperature oxidation protection and corrosion protection.
  • corresponding components such as turbine blades of aircraft engines and in particular low-pressure turbine blades.
  • the present invention is based on the idea that and an improved corrosion protection effect can be achieved with sufficient oxidation protection when a layer system with a very high chromium content and a simultaneously increased aluminum content is produced.
  • the coating can be produced by a two-stage process in which a chromium-rich layer is first produced by chromium plating in order subsequently to produce a significant aluminum content in the layer by alitizing.
  • the coating system or the method is used in components for gas turbines or aircraft engines, such components may preferably consist of nickel-based alloys, so that a portion of the layer system produced by constituents of the base material, ie in particular nickel as the main component with the largest proportion of the alloy, is formed.
  • nickel-base alloys iron or cobalt-base alloys are also suitable, so that the coating can also have corresponding proportions of iron and / or cobalt.
  • the coating comprises an outer and an inner zone.
  • the outer zone of the coating is biphasic.
  • the at least two-phase or bimodal microstructure comprises a chromium-rich ⁇ phase embedded in a matrix of the main component of the alloy of the coated component, chromium and aluminum, while the inner zone is a mixed crystal zone having the same constituents.
  • the coating may preferably have more than 30% by weight of chromium, in particular 35% by weight to 90% by weight of chromium, preferably 40% by weight to 60% by weight, of chromium over the entire coating.
  • the chromium content is higher and may range from 40% to 95% by weight.
  • chromium content in the ⁇ -chromium phases may be greater than or equal to 70 wt .-%, preferably greater than or equal to 80 wt .-%.
  • the aluminum content may be in the outer zone and / or over the entire coating in the range of 10 to 40 wt .-%, preferably 15 to 30 wt .-%, in particular 20 to 25 wt .-% aluminum.
  • the respective remainder is formed by constituents of the base material, in which the layer has at least partially grown in by diffusion, and / or which have diffused into the coating.
  • nickel-base alloys which can be used in gas turbine construction and in aircraft engines for temperature-stressed components
  • nickel-containing phase components such as, for example, aluminum-nickel-chromium phases
  • the matrix of the outer zone and / or the inner mixed crystal zone may comprise a mixture of mixed crystals formed from the main component of the alloy of the coated component and / or aluminum and / or chromium, as for example in a nickel-based alloy Al x Ni y , AlNi , Al 3 Ni 2, Al 3 Ni 2 Al or Cr.
  • the outer zone may account for more than or equal to 50% of the total coating coverage.
  • the ⁇ -chromium phases can be present as globulitic or ellipsoidal grains and have a volume fraction in the outer zone of 10 to 90% by volume.
  • the average grain diameter that is to say in the case of a non-circular shape, for example the mean value of minimum and maximum diameter, can be in the range of 2 ⁇ m and 40 ⁇ m.
  • the coating may have oxides in a proportion of 1 wt .-% to 15 wt .-%, which may have an average grain diameter of 2 microns to 20 microns.
  • the layer thickness of the coating can be in the range from 20 ⁇ m to 150 ⁇ m.
  • the chromating step in the two-step process for producing high chromium-containing high aluminum content layers can be carried out by inch-chromizing processes such as powder packing or gas phase inchromination wherein the chromium chemical activity is greater than or equal to 0.4.
  • the chromation may be produced by a temperature treatment in the presence of chromium powder pack and halide-containing atmosphere, which powder pack may comprise activators and binders.
  • powder pack may comprise activators and binders.
  • binders are alcohols or other
  • chromium powder pack with chromium activities (chemical activity) of more than 0.4 or 40% when stored in a temperature range of 1050 ° C to 1180 ° C, especially 1090 ° C to 1100 ° C for times of 2 up to 20 hours, in particular 10 to 15 hours, a chromium-rich layer with a layer thickness of 10 .mu.m to 150 .mu.m and a chromium content of greater than or equal to 40 wt .-%, in particular 50 wt .-% to 95 wt .-% are formed.
  • the chromium-rich layer has an outer ⁇ -chromium sublayer and an inner mixed crystal layer comprising substantially chromium and the major component of the alloy of the coated component, e.g. Nickel on.
  • the base material thus treated for example a component of a gas turbine or an aircraft engine, subjected to an Alitiermaschine (also gas phase Alit réelle), in which the component, for example, in a powder package with high aluminum activity (chemical activity) in the range or greater equal to 0.3 or 30% and stored at temperatures in the range of 1050 ° C to 1150 ° C, preferably 1080 ° C to 1100 ° C for 3 to 20 hours, especially 9 to 15 hours, outsourced.
  • Suitable powder packings are mixtures of aluminum oxide powder, aluminum powder and a halide activator, so that aluminum in the order of 10% by weight to 30% by weight can diffuse into the layer.
  • a second alitization may be carried out with a lower chemical aluminum activity, the aluminum activity being selectable in the range of 0.05 to 0.3.
  • the aging temperature in this second Alitier Marin may be greater than or equal to 1050 ° C and the aging time 3 to 20 hours.
  • a diffusion annealing may be performed at a temperature greater than or equal to 1050 ° C. for a period of 2 to 8 hours.
  • Surface treatment may be performed by physical vapor deposition (PVD), chemical vapor deposition (CVD), painting, electrodeposition and / or direct application of a substance before, during or after chromating and / or alitizing.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • electrodeposition electrodeposition and / or direct application of a substance before, during or after chromating and / or alitizing.
  • one or more elements from the group, the platinum, palladium, hafnium, zirconium, yttrium and Silicon comprises be applied.
  • these elements can be introduced into the layer so as to additionally influence the layer properties positively.
  • the Fig. 1 Figure 11 is a ternary phase diagram illustrating the region of the composition in which to place the coating applied to a nickel base material according to the present invention.
  • the hatched box shows the range of composition that the coating according to the invention may have. It is here a high chromium content of more than 30 wt .-% chromium, in particular in the range of 30 to 90 wt .-% chromium and an average aluminum content of 10 to 35 wt .-% aluminum before.
  • the proportion of the base material or the main component thereof is less than 30 wt .-%, ie in the present case less than 30 wt .-% nickel.
  • FIG. 15 shows the formation of a chromium-rich layer after high-activity chromizing wherein an outer ⁇ -chromium-nickel sublayer and a chromium-containing mixed crystal sublayer are formed.
  • the mixed crystal sublayer is formed by mixed crystals of chromium and the main component of the base material, for example NiCr when applied to nickel-base alloys.
  • the chromium rich layer of the ⁇ - chromium - nickel partial layer and the Mixed crystal layer has a chromium content of greater than or equal to 40 wt .-%.
  • elements of the base material and / or selectively introduced platinum and palladium, silicon, hafnium, yttrium and / or zirconium may be present.
  • the component with a correspondingly formed intermediate layer is subjected to an Alitier Colour in a second step, wherein aluminum diffuses into the intermediate layer, so that an AlNiCr matrix is formed in the ⁇ - chromium phases are embedded in an outer zone, such as FIG. 3 is shown.
  • the ⁇ -chromium phases can have a Cr content of more than 40% by weight, the remainder being essentially nickel.
  • the outer zone with the bimodal microstructure accounts for more than 60% of the total layer thickness.
  • the inner zone comprises only one NiAlCr mixed crystal having a composition of more than 30% by weight of nickel, less than 40% by weight of Cr, and less than 30% by weight of Al.
  • the ⁇ -chromium phase has a volume fraction of 10-90% and in the precipitation form is globolitic and ellipsoidal with a diameter of 1 to 40 ⁇ m.
  • the AlCrNi phase has 90% by volume.
  • the AlNiCr matrix of the outer zone comprises in particular Al x Ni y , AlNi, Al 3 Ni 2 , Al 3 Ni and Cr 2 Al phases, while in the NiAlCr mixed crystal zone of the inner zone substantially NiAl mixed crystals with chromium components are present.
  • the ⁇ -chromium phase of the outer zone has chromium contents of greater than or equal to 70% by weight of chromium, with essentially additional nickel being dissolved in the ⁇ -chromium phases.
  • the total layer has a chemical composition of chromium 30 to 90% by weight, aluminum 10 to 35% by weight, nickel to 60% by weight, proportions of platinum, palladium up to 25% by weight, silicon up to 15% by weight, Hafnium, zirconium up to 15% by weight.
  • the total layer thickness can be from 20 to 150 ⁇ m.

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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)
  • Chemical Treatment Of Metals (AREA)
EP13178306.0A 2012-08-08 2013-07-29 Revêtement CrAl à phases duplex pour une meilleure protection contre la corrosion/l'oxydation Withdrawn EP2695965A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102012015586.7A DE102012015586A1 (de) 2012-08-08 2012-08-08 Duplex Phasen CrAl-Beschichtung für verbesserten Korrosions-/Oxidations-Schutz

Publications (2)

Publication Number Publication Date
EP2695965A2 true EP2695965A2 (fr) 2014-02-12
EP2695965A3 EP2695965A3 (fr) 2017-03-29

Family

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EP13178306.0A Withdrawn EP2695965A3 (fr) 2012-08-08 2013-07-29 Revêtement CrAl à phases duplex pour une meilleure protection contre la corrosion/l'oxydation

Country Status (3)

Country Link
US (1) US9689270B2 (fr)
EP (1) EP2695965A3 (fr)
DE (1) DE102012015586A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3438414A1 (fr) * 2017-08-04 2019-02-06 MTU Aero Engines GmbH Aube pour turbomachine dotée des différentes couches de protection et procédé de fabrication

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10378118B2 (en) 2013-12-11 2019-08-13 United Technologies Corporation Electroformed nickel-chromium alloy
US9970094B2 (en) * 2014-01-14 2018-05-15 Praxair S.T. Technology, Inc. Modified slurry compositions for forming improved chromium diffusion coatings
JP6528926B2 (ja) 2014-05-21 2019-06-12 株式会社Ihi 原子力施設の回転機器
DE102014222024A1 (de) 2014-10-29 2016-06-16 MTU Aero Engines AG Schlicker und Verfahren zur Herstellung einer Oxidations- und Korrosionsbeständigen Diffusionschicht
US9909019B2 (en) 2015-06-24 2018-03-06 General Electric Company Diffusion coatings for metal-based substrate and methods of preparation thereof
DE102016103664A1 (de) * 2016-03-01 2017-09-07 Lufthansa Technik Ag Strömungselement und Verfahren zum Beschichten eines Strömungselements
US10053779B2 (en) 2016-06-22 2018-08-21 General Electric Company Coating process for applying a bifurcated coating
US10077494B2 (en) 2016-09-13 2018-09-18 General Electric Company Process for forming diffusion coating on substrate
WO2020188321A1 (fr) * 2019-03-20 2020-09-24 Arcelormittal Substrat en acier revêtu, procédé de fabrication d'un substrat en acier revêtu, procédé de fabrication d'un produit en acier et produit en acier
GB202112262D0 (en) * 2021-08-27 2021-10-13 Johnson Matthey Plc Process

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US3290126A (en) * 1965-04-29 1966-12-06 Du Pont Protectively coated nickel or cobalt articles and process of making
WO2006026456A1 (fr) 2004-08-26 2006-03-09 Honeywell International Inc. Chrome et revêtements aluminure platine modifiés d’éléments actifs
DE102008039969A1 (de) 2008-08-27 2010-03-04 Mtu Aero Engines Gmbh Turbinenschaufel einer Gasturbine und Verfahren zum Beschichten einer Turbinenschaufel einer Gasturbine

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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3290126A (en) * 1965-04-29 1966-12-06 Du Pont Protectively coated nickel or cobalt articles and process of making
WO2006026456A1 (fr) 2004-08-26 2006-03-09 Honeywell International Inc. Chrome et revêtements aluminure platine modifiés d’éléments actifs
DE102008039969A1 (de) 2008-08-27 2010-03-04 Mtu Aero Engines Gmbh Turbinenschaufel einer Gasturbine und Verfahren zum Beschichten einer Turbinenschaufel einer Gasturbine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3438414A1 (fr) * 2017-08-04 2019-02-06 MTU Aero Engines GmbH Aube pour turbomachine dotée des différentes couches de protection et procédé de fabrication
US10914181B2 (en) 2017-08-04 2021-02-09 MTU Aero Engines AG Blade or vane for turbomachine with different diffusion protective coatings and method for manufacture thereof

Also Published As

Publication number Publication date
US20140044986A1 (en) 2014-02-13
EP2695965A3 (fr) 2017-03-29
DE102012015586A1 (de) 2014-05-15
US9689270B2 (en) 2017-06-27

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