EP1466037B1 - Hochtemperatur-schutzschicht - Google Patents

Hochtemperatur-schutzschicht Download PDF

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Publication number
EP1466037B1
EP1466037B1 EP03700010A EP03700010A EP1466037B1 EP 1466037 B1 EP1466037 B1 EP 1466037B1 EP 03700010 A EP03700010 A EP 03700010A EP 03700010 A EP03700010 A EP 03700010A EP 1466037 B1 EP1466037 B1 EP 1466037B1
Authority
EP
European Patent Office
Prior art keywords
protection layer
temperature protection
temperature
coating
layer
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.)
Expired - Lifetime
Application number
EP03700010A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1466037A1 (de
Inventor
Dietrich Eckardt
Klaus Erich Schneider
Christoph Toennes
Hans-Peter Bossmann
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.)
General Electric Technology GmbH
Original Assignee
Alstom Technology 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 Alstom Technology AG filed Critical Alstom Technology AG
Publication of EP1466037A1 publication Critical patent/EP1466037A1/de
Application granted granted Critical
Publication of EP1466037B1 publication Critical patent/EP1466037B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the invention relates to a high-temperature protective layer according to the independent Claim.
  • Such high-temperature protective layers are mainly used where the base material of components made of heat-resistant steels and / or alloys which is used at temperatures above 600 oC.
  • Such high temperature protective layers Due to these high-temperature protective layers, the effect of high-temperature corrosion especially of sulfur, oil pockets, oxygen, alkaline earths and vanadium slowed down or completely stopped.
  • Such high temperature protective layers are designed to be directly on the base material of the protective component can be applied.
  • high temperature protective coatings are of particular importance Importance. They are mainly used on runners and vanes as well Applied thermal heat segments of gas turbines.
  • these components is preferably an austenitic material used on the basis of nickel, cobalt or iron.
  • nickel superalloys are used as base material Application.
  • Most of the coatings for high temperature applications come from the Families of NiCrAlY, CoCrAlY or NiCoCrAlY.
  • the layers are different through the concentration of "family elements" nickel, cobalt, chrome, aluminum and Yttrium and by adding more elements.
  • the composition of the layer determined Significantly, the behavior at high temperature in oxidizing or corrosive Atmosphere, with temperature changes and under mechanical load. moreover the composition of the layer determines the material and manufacturing costs.
  • Many known layers show excellent properties only in some aspects. Although widely used worldwide, by adding cobalt according to their own Investigations have negatively affected both corrosion resistance and cost.
  • the invention is based on the above-mentioned prior art the The object of the invention is to provide a high-temperature protective layer which is cost-effective, resistant to oxidation, corrosion and temperature change resistant.
  • the inventive composition of this alloy has (wt .-%) 23 bis 27% chromium, 4 to 7% aluminum, 0.1 to 3% silicon, 0.1 to 3% tantalum, 0.2 to 2% Yttrium, 0.001 to 0.01% boron, 0.001 to 0.01% magnesium and 0.001 to 0.01% calcium on. All weights are based on the total weight of the respective Alloy. The remainder of the alloy is nickel and unavoidable Impurities.
  • the Al content is in a range of more than 5 to 6 Wt .-%.
  • the protective layer according to the invention is a NiCrAlY alloy. It shows a significant improvement in oxidation and corrosion resistance compared to the already known high-temperature protective layers.
  • the high-temperature protective layer according to the invention it should be noted that they at high temperatures (depending on the design above 800 ° C) aluminum-containing ⁇ and ⁇ '-phases having a volume fraction of at least 50%, which the Formation of an aluminum oxide-containing protective layer allows, at low and at medium temperatures (depending on the design below 900 ° C) chromium-containing ⁇ -Cr phases (referred to in Fig. 1 as BCC) of more than 5%, which the training a chromium oxide-containing protective layer allows.
  • BCC chromium-containing ⁇ -Cr phases
  • the adhesion of the alumina-containing cover layer improves High temperature, which is the protection of the high-temperature protective layer and the underneath located significantly increased component.
  • magnesium and calcium are especially the naturally occurring impurities in the production bound and thus for temperatures below 850-950 ° C the Increased corrosion resistance.
  • the amount ratio of chromium to aluminum is limited to 3.6 to 6.5 to prevent the formation of brittle ⁇ -phases.
  • the ratio of nickel to chromium is limited to 2.3 to 3.0 in order to obtain brittle ⁇ phases to prevent what improves the thermal shock resistance.
  • the solid and the consistent adhesion of the protective layer and its topcoat in frequent Temperature change is due to the specified for the alloy share Yttrium reached.
  • composition chosen here shows no or only small proportions by volume of ⁇ -phase or ⁇ -NiAl phase (FIG. 1), so that under thermal cycling clearly advantages are to be expected.
  • the comparative alloy of Fig. 2 shows a similar one Composition of some elements, but due to the differences of others Elements show a very different microstructure based on In our experience, no adequate thermal shock resistance for turbine and can not be used by the incipient melting over 900 ° C. is.
  • the production-related, inherent contamination of sulfur which is typically in concentrations of less than 10 ppm, in some cases up to 50 ppm can lead to reduced oxidation and corrosion resistance.
  • the trace elements Mg and Ca added, which absorb sulfur.
  • the alloy is applied directly to the base material of the component or to an intermediate layer, consisting of a third composition, applied.
  • the layer thicknesses vary depending on the coating method between 0.03 mm to 1.5 mm.
  • the gas turbine component to be coated is made of an austenitic material, in particular a nickel superalloy.
  • the coating of the component takes place under Vacuum, under inert gas or in air by means of thermal spraying (LPPS, VPS, APS), high speed spraying (HVOF), electrochemical processes, physical / chemical vaporization (PVD, CVD) or another from the Prior art known coating method.
  • a NiCrAlY alloy is used according to the invention (Wt .-%) 23 to 27 wt .-% chromium, 4 to 7 wt .-% aluminum, 0.1 to 3 wt .-% silicon, 0.1 to 3% by weight of tantalum, 0.2 to 2% by weight of yttrium, 0.001 to 0.01% by weight of boron, 0.001 to 0.01% by weight of magnesium and 0.001 to 0.01% by weight of calcium.
  • the remaining portion of the alloy consists of nickel and unavoidable impurities.
  • the Al content is in a range of over 5 to 6 wt .-%. All weights refer to the total weight of the alloy used.
  • the alloy according to the invention has a marked improvement in the oxidation and corrosion resistance over the already known high-temperature protective layers on.
  • inventive high-temperature protective layer is determine that they are at high temperatures (depending on the design above 800 ° C) aluminum-containing ⁇ and ⁇ '-phases with a volume fraction of at least 50%, which allows the formation of an aluminum oxide-containing protective layer, at low and medium temperatures (depending on the version below of 900 ° C) chromium-containing ⁇ -Cr phases of more than 5%, which the training a chromium oxide-containing protective layer allows.
  • the composition selected here shows no or only small volume fractions of ⁇ -phase or ⁇ -NiAl phase or boride phases (in Fig. 1 as M2B_ORTH), so that under thermal cycling significant benefits are expected.
  • the comparative alloy ( Figure 2) shows a similar one Composition of some elements, but due to the differences of others Elements show a very different microstructure based on In our experience, no adequate thermal shock resistance for turbine and can not be used by the incipient melting over 900 ° C. is.
  • the base material that forms the high-temperature protective layer silicon and boron added. This increases the protection of the high-temperature protective layer and the underlying device essential.
  • the production-related, inherent contamination of sulfur which is typically in a concentration of less than 10 ppm, in some cases 50 ppm can lead to reduced oxidation and corrosion resistance.
  • the trace elements Mg and Ca are added, which absorb sulfur and thereby in for temperatures below from 850 to 950 ° C increases the corrosion resistance.
  • the ratio of chromium to aluminum is limited to 3.6 to 6.5 to the Prevent training of brittle ⁇ -phases.
  • the ratio of nickel to Chromium is limited to 2.3 to 3.0, to prevent brittle ⁇ -phases, what the thermal shock resistance improved.
  • the firm and consistent adhesion of the protective layer and its topcoat Frequent temperature change is determined by the specific for the alloy Proportion of yttrium reached.
  • the material forming the alloy is in powder form for the thermal spraying processes before and preferably has a particle size of 5 to 90 microns.
  • the alloy is prepared as a target or as a suspension.
  • the alloy is applied directly to the base material of the component or to an intermediate layer, consisting of a third composition, applied.
  • the layer thicknesses vary depending on the coating method between 0.03 mm to 1.5 mm.
  • the device is subjected to a heat treatment. This takes place at a temperature of 1000 to 1200 ° C for about 10 minutes up to 24 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Inorganic Insulating Materials (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Organic Insulating Materials (AREA)
  • Magnetic Heads (AREA)
  • Physical Vapour Deposition (AREA)
  • Spark Plugs (AREA)
  • Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Resistance Heating (AREA)
  • Ceramic Products (AREA)
EP03700010A 2002-01-18 2003-01-16 Hochtemperatur-schutzschicht Expired - Lifetime EP1466037B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10202012 2002-01-18
DE10202012 2002-01-18
PCT/CH2003/000023 WO2003060194A1 (de) 2002-01-18 2003-01-16 Hochtemperatur-schutzschicht

Publications (2)

Publication Number Publication Date
EP1466037A1 EP1466037A1 (de) 2004-10-13
EP1466037B1 true EP1466037B1 (de) 2005-07-13

Family

ID=7712588

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03700010A Expired - Lifetime EP1466037B1 (de) 2002-01-18 2003-01-16 Hochtemperatur-schutzschicht

Country Status (12)

Country Link
US (1) US7052782B2 (ja)
EP (1) EP1466037B1 (ja)
JP (1) JP4217626B2 (ja)
CN (1) CN100350075C (ja)
AT (1) ATE299536T1 (ja)
AU (1) AU2003200835A1 (ja)
BR (1) BR0306989B1 (ja)
CA (1) CA2473565C (ja)
DE (1) DE50300758D1 (ja)
ES (1) ES2244914T3 (ja)
RU (1) RU2301284C2 (ja)
WO (1) WO2003060194A1 (ja)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50300758D1 (de) 2002-01-18 2005-08-18 Alstom Technology Ltd Baden Hochtemperatur-schutzschicht
US7288328B2 (en) * 2004-10-29 2007-10-30 General Electric Company Superalloy article having a gamma-prime nickel aluminide coating
US7364801B1 (en) * 2006-12-06 2008-04-29 General Electric Company Turbine component protected with environmental coating
IL191822A0 (en) * 2007-06-25 2009-02-11 Sulzer Metaplas Gmbh Layer system for the formation of a surface layer on a surface of a substrate and also are vaporization source for the manufacture of a layer system
EP2022870B1 (de) * 2007-06-25 2014-07-23 Sulzer Metaplas GmbH Schichtsystem zur Bildung einer Oberflächenschicht auf einer Oberfläche eines Substrats, sowie Verdampfungsquelle zur Herstellung eines Schichtsystems
US20110059323A1 (en) * 2008-03-04 2011-03-10 Friedhelm Schmitz Alloy, high-temperature corrosion protection layer and layer system
DE102010021691A1 (de) * 2010-05-27 2011-12-01 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Schichtverbund mit einer eindimensionalen Kompositstruktur
EP2474413A1 (de) * 2011-01-06 2012-07-11 Siemens Aktiengesellschaft Legierung, Schutzschicht und Bauteil
US9359669B2 (en) * 2011-12-09 2016-06-07 United Technologies Corporation Method for improved cathodic arc coating process
EP3118345B1 (en) * 2015-07-17 2018-04-11 Ansaldo Energia IP UK Limited High temperature protective coating
CN105419409A (zh) * 2015-11-23 2016-03-23 沈阳黎明航空发动机(集团)有限责任公司 一种抗高温燃气冲刷涂料及其制备方法和应用
CN108165902A (zh) * 2017-12-27 2018-06-15 宁波市江北吉铭汽车配件有限公司 一种贮油桶
CA3129143A1 (en) * 2019-03-07 2020-09-10 Oerlikon Metco (Us) Inc. Advanced bond coat materials for tbc with improved thermal cyclic fatigue and sulfidation resistance
CN111485205A (zh) * 2020-05-25 2020-08-04 中国科学院宁波材料技术与工程研究所 一种NiMAlY/Al2O3复合涂层及其制备方法与应用

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US3754903A (en) 1970-09-15 1973-08-28 United Aircraft Corp High temperature oxidation resistant coating alloy
US4013424A (en) 1971-06-19 1977-03-22 Rolls-Royce (1971) Limited Composite articles
US3837894A (en) 1972-05-22 1974-09-24 Union Carbide Corp Process for producing a corrosion resistant duplex coating
US4022587A (en) 1974-04-24 1977-05-10 Cabot Corporation Protective nickel base alloy coatings
US4088479A (en) 1976-01-16 1978-05-09 Westinghouse Electric Corp. Hot corrosion resistant fabricable alloy
US4095003A (en) 1976-09-09 1978-06-13 Union Carbide Corporation Duplex coating for thermal and corrosion protection
JPS5385736A (en) * 1977-01-06 1978-07-28 Mitsubishi Heavy Ind Ltd Surface treatment method of metallic body
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DE3246507C2 (de) 1982-12-16 1987-04-09 BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau Hochtemperaturschutzschicht
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
DE3740478C1 (de) 1987-11-28 1989-01-19 Asea Brown Boveri Hochtemperatur-Schutzschicht
IT1294098B1 (it) * 1997-07-10 1999-03-22 Flametal S P A Lega per rivestimenti o riporti resistenti alla corrosione.
EP1001055B1 (en) * 1998-11-10 2004-02-25 ALSTOM Technology Ltd Gas turbine component
KR100372482B1 (ko) * 1999-06-30 2003-02-17 스미토모 긴조쿠 고교 가부시키가이샤 니켈 베이스 내열합금
JP3952861B2 (ja) * 2001-06-19 2007-08-01 住友金属工業株式会社 耐メタルダスティング性を有する金属材料
DE50300758D1 (de) 2002-01-18 2005-08-18 Alstom Technology Ltd Baden Hochtemperatur-schutzschicht

Also Published As

Publication number Publication date
BR0306989B1 (pt) 2012-03-06
CA2473565A1 (en) 2003-07-24
WO2003060194A1 (de) 2003-07-24
ES2244914T3 (es) 2005-12-16
AU2003200835A1 (en) 2003-07-30
US20050042474A1 (en) 2005-02-24
RU2004125154A (ru) 2005-07-20
RU2301284C2 (ru) 2007-06-20
CN1617951A (zh) 2005-05-18
EP1466037A1 (de) 2004-10-13
DE50300758D1 (de) 2005-08-18
BR0306989A (pt) 2004-12-14
CN100350075C (zh) 2007-11-21
ATE299536T1 (de) 2005-07-15
JP4217626B2 (ja) 2009-02-04
US7052782B2 (en) 2006-05-30
JP2005514525A (ja) 2005-05-19
CA2473565C (en) 2010-12-07

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