CA2011753A1 - Structural element with protective coating on nickel or cobalt - Google Patents

Structural element with protective coating on nickel or cobalt

Info

Publication number
CA2011753A1
CA2011753A1 CA002011753A CA2011753A CA2011753A1 CA 2011753 A1 CA2011753 A1 CA 2011753A1 CA 002011753 A CA002011753 A CA 002011753A CA 2011753 A CA2011753 A CA 2011753A CA 2011753 A1 CA2011753 A1 CA 2011753A1
Authority
CA
Canada
Prior art keywords
basic material
protective coating
coating
component
grain
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.)
Abandoned
Application number
CA002011753A
Other languages
French (fr)
Inventor
Albin Platz
Klaus Schweitzer
Peter Adam
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 GmbH
Original Assignee
Albin Platz
Klaus Schweitzer
Peter Adam
Mtu Motoren- Und Turbinen-Union Munchen Gmbh
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 Albin Platz, Klaus Schweitzer, Peter Adam, Mtu Motoren- Und Turbinen-Union Munchen Gmbh filed Critical Albin Platz
Publication of CA2011753A1 publication Critical patent/CA2011753A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12Blades
    • F01D5/28Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288Protective coatings for blades

Abstract

Abstract The present invention relates to a component of a basic material based on nickel or cobalt, which has a coating to provide it with protection against oxidation, corrosion, and thermal fatigue, the protective coating and the basic material being of the same chemical composition. This enhances the adhesion of the protective coating, reduces the tendency to crack, and improves its resistance to thermal fatigue.

Description

20117~3 The present invention relates to a component of a basic material that is based on nickel or cobalt, which has a coating to protect it against oxidation, corrosion, and thermal fatigue.

Super alloys that are resistant to high temperatures, and are based on nickel or cobalt, were developed for use in turbine construction. The material used in the blades is exposed to particularly high stress levels; the blades have to be able to withstand not only the high temperatures (in excess of 950C) within the turbine, but must also possess a high level of creep resistance. In order to ensure a higher order of creep resistance, the material used for the blades is grown with large crystals and in part with a columnar structure, from super alloys, by suitable casting and crystallization techniques. It is a disadvantage for corrosion resistance that during this growth, grain boundary deposits of easily oxidized alloy additives, such as vanadium or titanium, for example, are formed. This causes a disadvantageous deterioration of the surface properties such as resistance to oxidation and corrosion, as well as resistance to thermal fatigue. For this reason, coatings such as the MCrAlX,Y
family have been developed (metal, chromium, aluminum, X =
rare earths, Y = yttrium); these improve the surface properties by virtue of their high chromium and aluminum contents which, for their part, form stable oxides during operation of the turbine, and which, as a result of the rare earth metals, improve the adhesion of the oxide layer to the surface coating.

Diffusion processes are disadvantageous because of the different concentrations on both sides of the boundary layer between the coating surface and the coating, which lead to diffusion pores in the area close to the boundary layers, so that the protective coating bursts when thermal stresses are superimposed on points with higher densities of diffusion pores. Furthermore, the MCrAlX,Y coatings have a tendency to 20117~s~

thermal fatigue since there is a disparity in the thermal expansion behaviour between the basic material alloy and the MCrAlYX coating, and the MCrAlX,Y coatings are extremely ductile in comparison to the basic material.

A further known technical solution is the formation of chromium and/or aluminum-rich diffusion coatings on the surface of the basic material by powder pack cementing and/or gas diffusion coating. Coatings of this kind form oxidation-resistant intermetallic phases with the basic material.
Because of the increased hardness of these coatings with intermetallic phases, the fatigue limit of the components is disadvantageously reduced by up to 30 per cent. Since the thermal expansion behaviour is not adapted to the basic material, there is an increased risk of microcracks forming in the component, and this increases with increased thickness of the coating. For this reason, and most disadvantageously, the thickness of the coatings must be kept below 100 ~m.

In the case of the known coatings, components of the basic material that are sensitive to oxidation and corrosion, such as vanadium and titanium, are not used, and stable oxide-forming substances such as aluminum, up to 20 per cent, for example, and chromium up to 40 per cent, are added to form alloys. Matching the composition of the coating to the super-alloy based on cobalt or nickel that is to be coated becomes increasingly involved and more extensive in order to overcome problems of adhesion or to minimize diffusion processes, or to build up protective stable oxides on the surface.

It i~ an object of the present invention to describe a component produced from a basic material based on cobalt or nickel and with a protective coating, that displays greater resistance to thermal fatigue, oxidation, and corrosion at temperatures above 800C, than formerly known coatings and which overcomes the disadvantages of such coatings, and a process for producing such components.

This has been achieved in that the basic material and the protective coating are of the same chemically equal material, and the protective coating is structured with a much finer grain.

According to the present invention there is provided in a component of a basic material based on nickel or cobalt, with a protective coating of the same chemical composition to ensure protection against oxidation, corrosion, and thermal fatigue, the improvement wherein the protective coating is essentially structure with a finer grain than the basic material, and the lowest layer of the fine-grain coating exhibits the same crystal orientation as the large-volume crystallite of the basic material on the boundaries of the coating.

The present invention solves the problems and the disadvantages as they exist in the prior art, in that the substance for the basic material is used for a coating of a similar type, so that there are no diffusion processes and problems of adhesion do not occur when the surface of the basic material is free of oxide. Thus there is no bursting of the particles in the protective coating.

Because of a constant composition of the alloy in the grain volume, an even, stable and protective oxide layer will advantageously be formed on the grain surface when such components are used in an oxidizing flow of hot gas, as in a turbine, for example. Since the grain boundaries of this coating exhibit fewer grain boundary deposits than the basic material, grain boundary corrosion is advantageously reduced. -The preferred corrosion attack at the grain boundaries and the associated tendency to crack, is hindered by the 20117~3 which overcomes the disadvantages of such coatings, and a process for producing such components.

This has been achieved in that the basic material and the protective coating are of the same chemically equal material, and the protective coating is structured with a much finer grain.

According to the present invention there is provided in a component of a basic material based on nickel or cobalt, with a protective coating of the same chemical composition to ensure protection against oxidation, corrosion, and thermal fatigue, the improvement wherein the protective coating is essentially structure with a finer grain than the basic material, and the lowest layer of the fine-grain coating exhibits the same crystal orientation as the large-volume crystallite of the basic material on the boundaries of the cvating.

The present invention solves the problems and the disadvantages as they exist in the prior art, in that the substance for the basic material is used for a coating of a similar type, so that there are no diffusion processes and problems of adhesion do not occur when the surface of the basic material is free of oxide. Thus there is no bursting of the particles in the protective coating.

Because of a constant composition of the alloy in the grain volume, an even, stable and protective oxide layer will aclvantageously be formed on the grain surface when such components are used in an oxidizing flow of hot gas, as in a turbine, for example. Since the grain boundaries of this coating exhibit fewer grain boundary deposits than the basic material, grain boundary corrosion is advantageously reduced. ~-The preferred corrosion attack at the grain boundaries and the associated tendency to crack, is hindered by the 20117~3 this reason, the grain volume of the coating is preferably three powers of ten smaller than the grain volume of the basic material.

The grain boundaries of the preferred basic material IN 100 exhibit grain boundary deposits that contain titanium and vanadium, and these form unstable or low-melting point oxides. For this reason, the coating has fewer deposits on the grain boundaries than the basic material, and this advantageously improves resistance to oxidation and corrosion.

A preferred formation of the protective coating is such that the protective coating is a plasma-spray coating that crystallizes with an extremely fine grain and with small number of deposits because of its very high hardening speed.

In addition, present invention provides a process for the production of a component by the following process steps:
a) Surface preparation by removal of the surface of the basic material, this being done to improve adhesion;
b) Coating applied to the basic material by means of plasma spraying with plasma spra~ing material with the chemical composition of the basic material;
c) Epitactic recrystallisation by means of solution heat treatment at temperatures between 1150 and 1250C;
d) After-treatment of the surface of the protective coating 2S by mechanical consolidation for smoothing and strengthening of the surface and/or diffusion coatings to increase resistance to oxidation.

The process has the advantage that it is suitable for mass-production processes.

When increased demands made of the quality of the coating, the surface preparation is effected by plasma etching with argon plasma. This preparation entails the advantage of 201~7~3 freedom from contamination, and is compatible with a low-pressure plasma spraying process, so that both surface preparation and coating of the basic material can be effected on a component element with an assembly procedure. This enhances the quality so no move to another plant is needed, and no time is spent in a normal atmosphere.

In the event that there are increased demands for economy, the surface preparation can be effected by chemical removal, so that a higher throughput can be achieved.

An abrasive jet preparation is advantageously used as surface removal since large area components such a rotor disks can be prepared for subsequent coating by using this process.

In the case of increased demands for quality, coating can be effected by plasma spraying with plasma spraying material of the same chemical composition as the basic material; in the case of large components and/or in the event of higher demands for economy, this can be effected by plasma spraying in an atmosphere of protective gas.

An optimal accumulation of the coating on the basic material is achieved by epitactic recrystallisation at a solution heat treatment temperature between 1150 and 1250C. When this is done, the lowest position of the fine-grain coating recrystallises in the transition zone between the basic material and the coating, in the same crystal orientation as the large volume crystallite of the basic material on the coating boundary, so that intensive denticulation results between the fine-grain coating and the coarse-grain basic material, which greatly increases adhesion compared to conventional coatings of different kinds. Then, the coated components can be cooled from 1000C to 800C at 30C/minute to 80C/minute and subjected to a multi-stage thermal aging processingO

20117~3 For cast components of super-alloys based on nickel or cobalt a two-stage aging process for forming a suitable ~
structure at 1080C to 1120C for 2 hours to 6 hours followed by 900 to 980C for 10 hours to 20 hours, with intermediate cooling at 750C to 800C. This type of thermal treatment regenerates the properties of the basic material that have been altered by the solution heat treatment, and the strength values of the coating are advantageously enhanced thereby.

Mechanical after-treatment of the surface of the protective coating improves the hardness by preferably shot-blasting, as serves to smooth the surface. The smoothing of the surface can also be effected by means of vibratory grinding or Druckfliess processing.

Diffusion coating as an after-treatment of the surface, as is usually applied to the basic material of super-alloys that are based on nickel or cobalt in order to increase long-term resistance to oxidation can advantageously be effected on the fine-grain coating. This entails the advantage that deep diffusions, as they occur along the grain boundary deposits of the basic material, do not occur in the fine-grain coatings with fewer grain-boundary deposits. The diffusion zone in the fine-grain coating is thus more even and homogeneous when doped, for example, with aluminum or chromium, than is possible on the coarse crystalline basic material. When this is done, the chromium doping improves the resistance to oxidation up to temperatures of 850C, and at the same time, brings about enhanced resistance to corrosion caused by sulfidation. Doping with aluminum, for example, increas~s resistance to oxidation at temperatures of up to 1250C.

The following examples of applications for a component and a process represent preferred embodiments of the present invention.

201~7~3 Example of a component:

A low-pressure plasma coating of the same chemical composition, which has a 3-103-times smaller grain volume than the basic material, was applied on a coarse-crystalline turbine blade of IN 100 as the basic material, which was composed as follows:

13 to 17 %-wt Co 8 to 11 %-wt Cr to 6 %-wt Al 4.5 to 5 %-wt Ti 2 to 4 %-wt Mo 0.~ to 1.2 %-wt V
0.15 to 0.2 %-wt C
0.01 to 0.02 %-wt B
0~03 to 0.09 %-wt Zr Remainder Ni During thermal-fatigue testing (test temperature 1050DC) the coated component exhibited a temperature-endurance three times greater than that of the uncoated basic material.

Example of a process In a coarse-crystalline turbine blade of IN 100 as the basic material, composed of the following elements 13 to 17 %-wt Co 8 to 11 %-wt Cr 5 to 6 %-wt ~1 4.5 to 5 %-wt Ti 2 to 4 %-wt Mo 0.7 to 1.2 %-wt V
0.15 to 0.2 % w~ C
0.01 to 0.02 %-wt B
0.03 to 0.09 %-wt Zr 201~

Remainder Ni the surface of the basic material was removed on average to a depth of 0.5 to 10 ~m by means of argon~plasma etching at a pressure of 2 kPa to 4 kPa.

Next, the basic material was coated with plasma spray material of the same chemical composition as the basic material, using plasma spray technology; this was done at a pressure of 4 kP~ and at a temperature of the basic material of 900C, for a period of 120 seconds.

After the removal of the coated turbine blade, epitactic recrysallisation was effected in a high-vacuum oven. To this end, the component was maintained at a solution heat treatment temperature of 1200C for 4 hours, and cooled to 80C at a rate of 60C/minute.

In order to regenerate the strength characteristics of the basic material and to enhance the strength of the coating, a two-state heat treatment was completed in a high vacuum at 1100C for 4 hours and at 950C for 16 hours, with intermediate cooling to 800C at 60C/minute.

After cooling to room temperature, the surface of the component was smoothed and consolidated by shot peening with zirconium oxide pellets 0.5 to 1.0 mm diameter.

Claims (10)

1. In a component of a basic material based on nickel or cobalt, with a protective coating of the same chemical composition to ensure protection against oxidation, corrosion, and thermal fatigue, the improvement wherein the protective coating is essentially structure with a finer grain than the basic material, and the lowest layer of the fine-grain coating exhibits the same crystal orientation as the large-volume crystallite of the basic material on the boundaries of the coating.
2. A component as claimed in claim 1, wherein the protective coating exhibits fewer grain-boundary deposits and a more constant composition of the alloy in the grain volume than in the basic material.
3. A component as claimed in claim 1, wherein the basic material and the protective coating have the following composition:

13 to 17 %-wt Co 8 to 11 %-wt Cr to 6 %-wt Al
4.5 to 5 %-wt Ti 2 to 4 %-wt Mo 0.7 to 1.2 %-wt V
0.15 to 0.2 %-wt C
0.01 to 0.02 %-wt B
0.03 to 0.09 %-wt Zr Remainder Ni 4. A component as claimed in any one of claims 1 to 3, wherein the protective coating exhibits a grain volume that is three powers of ten finer than the basic material.
5. A component as claimed in any one of claims 1 to 3, wherein the protective coating has fewer vanadium or titanium deposits on the grain boundaries than the basic material with an equal vanadium or titanium content.
6. A component as claimed in any one of claims 1 to 3, wherein the protective coating is a plasma spray coating.
7. A process for the production of a component of a basic material based on nickel or cobalt, with a protective coating of the same chemical composition to ensure protection against oxidation, corrosion, and thermal fatigue, comprising the steps of:
a) pre-treating the surface of the component by removal of the surface of the basic material so as to improve adhesion;
b) coating the basic material by plasma spraying using plasma-spray material that is of the same chemical composition as the basic material;
c) carrying out epitactic recrystallisation by means of solution heat treatment at temperatures between 1150°C and 1250°C ; and d) carrying out after-treatment of the surface of the protective coating by mechanical consolidation to smooth and strengthen the surface and/or the diffusion coatings so as to increase resistance to oxidation.
8. A process as claimed in claim 7, wherein removal is effected by means of chemical etching, plasma etching, or abrasive jet processing such as shot peening.
9. A component as claimed in claim 7 or 8, wherein the surface of the protective coating is processed by a jet process to increase hardness and/or pressure-flow lapping and/or vibratory grinding.
10. A component as claimed in any one of claims 1 to 3, wherein the surface of the protective coating is subjected to after-treatment with a diffusion coating with aluminum and/or chromium.
CA002011753A 1989-03-09 1990-03-08 Structural element with protective coating on nickel or cobalt Abandoned CA2011753A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3907625A DE3907625C1 (en) 1989-03-09 1989-03-09
DEP3907625.3 1989-03-09

Publications (1)

Publication Number Publication Date
CA2011753A1 true CA2011753A1 (en) 1990-09-09

Family

ID=6375923

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002011753A Abandoned CA2011753A1 (en) 1989-03-09 1990-03-08 Structural element with protective coating on nickel or cobalt

Country Status (4)

Country Link
EP (1) EP0386618B1 (en)
JP (1) JPH02277760A (en)
CA (1) CA2011753A1 (en)
DE (1) DE3907625C1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2950436B2 (en) * 1990-03-15 1999-09-20 株式会社東芝 Manufacturing method of composite material
US5316866A (en) * 1991-09-09 1994-05-31 General Electric Company Strengthened protective coatings for superalloys
EP0840809B1 (en) * 1995-07-25 1999-04-21 Siemens Aktiengesellschaft Product with a metallic base body provided with cooling channels and its manufacture
US5881972A (en) * 1997-03-05 1999-03-16 United Technologies Corporation Electroformed sheath and airfoiled component construction
EP1162284A1 (en) 2000-06-05 2001-12-12 Alstom (Switzerland) Ltd Process of repairing a coated component
DE102004050474A1 (en) 2004-10-16 2006-04-20 Mtu Aero Engines Gmbh Process for producing a component coated with a wear protection coating
DE102011087159B3 (en) * 2011-11-25 2013-03-28 Mtu Aero Engines Gmbh Priming preparation for cold gas spraying and cold gas spraying device
JP5925958B2 (en) * 2013-09-25 2016-05-25 中国電力株式会社 Diffusion / penetration method of creep reinforcement for heat-resistant metal material member and method for producing heat-resistant metal material member with enhanced creep strength
KR102182699B1 (en) * 2014-11-11 2020-11-25 (주) 코미코 Internal member applying plasma treatment apparatus and method for manufacturing the same
KR102182690B1 (en) * 2014-11-11 2020-11-25 (주) 코미코 Internal member applying plasma treatment apparatus and method for manufacturing the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419416A (en) * 1981-08-05 1983-12-06 United Technologies Corporation Overlay coatings for superalloys
US4532191A (en) * 1982-09-22 1985-07-30 Exxon Research And Engineering Co. MCrAlY cladding layers and method for making same
DE3246507A1 (en) * 1982-12-16 1984-06-20 BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau HIGH TEMPERATURE PROTECTIVE LAYER
US4743514A (en) * 1983-06-29 1988-05-10 Allied-Signal Inc. Oxidation resistant protective coating system for gas turbine components, and process for preparation of coated components
DE3426201A1 (en) * 1984-07-17 1986-01-23 BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau PROCESS FOR APPLYING PROTECTIVE LAYERS
DE3683091D1 (en) * 1985-05-09 1992-02-06 United Technologies Corp PROTECTIVE LAYERS FOR SUPER ALLOYS, WELL ADAPTED TO THE SUBSTRATES.
DE3522646A1 (en) * 1985-06-25 1987-01-08 Wiederaufarbeitung Von Kernbre MOLDED BODY FROM BAD WELDABLE MATERIAL

Also Published As

Publication number Publication date
JPH02277760A (en) 1990-11-14
EP0386618B1 (en) 1994-02-16
EP0386618A1 (en) 1990-09-12
DE3907625C1 (en) 1990-02-15

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