EP1466037A1 - Revetement de protection haute temperature - Google Patents

Revetement de protection haute temperature

Info

Publication number
EP1466037A1
EP1466037A1 EP03700010A EP03700010A EP1466037A1 EP 1466037 A1 EP1466037 A1 EP 1466037A1 EP 03700010 A EP03700010 A EP 03700010A EP 03700010 A EP03700010 A EP 03700010A EP 1466037 A1 EP1466037 A1 EP 1466037A1
Authority
EP
European Patent Office
Prior art keywords
protective layer
temperature
temperature protective
layer according
coating
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.)
Granted
Application number
EP03700010A
Other languages
German (de)
English (en)
Other versions
EP1466037B1 (fr
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/fr
Application granted granted Critical
Publication of EP1466037B1 publication Critical patent/EP1466037B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 used above all where the base material of components made of heat-resistant steels and / or alloys that are used at temperatures above 600 S C is to be protected.
  • high-temperature protective layers are intended to slow down or completely prevent the effects of high-temperature corrosion, especially of sulfur, oil ash, oxygen, alkaline earths and vanadium.
  • Such high-temperature protective layers are designed so that they can be applied directly to the base material of the component to be protected.
  • High-temperature protective layers are of particular importance for components of gas turbines. They are mainly applied to rotor blades and guide vanes as well as to heat accumulation segments in gas turbines.
  • An austenitic material based on nickel, cobalt or iron is preferably used to manufacture these components.
  • nickel superalloys in particular are used as the base material.
  • the layers differ in the concentration of the "family elements" nickel, cobalt, chromium, aluminum and yttrium and in the addition of other elements.
  • the composition of the layer decisively determines the behavior at high temperature in an oxidizing or corrosive atmosphere, with temperature changes and with mechanical stress.
  • the composition of the layer determines the material and manufacturing costs.
  • Many known layers only show excellent properties in some aspects.Although widely used worldwide, the addition of cobalt has, according to our own investigations, negatively influenced both the corrosion resistance and the costs.
  • the invention is based on the object of creating a high-temperature protective layer which is inexpensive, oxidation-resistant, corrosion-resistant and resistant to temperature changes.
  • composition of this alloy according to the invention has (% by weight) 23 to 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. All weights refer to the total weight of the respective alloy. The rest of the alloy consists of nickel and unavoidable impurities. The Al content is preferably in a range from over 5 to 6% by weight.
  • the protective layer according to the invention is a NiCrAlY alloy. It shows a significant improvement in the resistance to oxidation and corrosion compared to the already known high-temperature protective layers.
  • the high-temperature protective layer according to the invention it can be ascertained that at high temperatures (depending on the version above 800 ° C.) it has aluminum-containing ⁇ and ⁇ ' phases with a volume fraction of at least 50%, which enables the formation of an aluminum oxide-containing protective layer, at low temperatures and at medium temperatures (depending on the version below 900 ° C.) has chromium-containing ⁇ -Cr phases (referred to as BCC in FIG. 1) of more than 5%, which enables the formation of a chromium oxide-containing protective layer.
  • BCC chromium-containing ⁇ -Cr phases
  • the adhesion of the aluminum oxide-containing cover layer at high temperature improves, which significantly increases the protection of the high-temperature protective layer and the component located underneath.
  • magnesium Calcium and calcium are primarily bound to the impurities that are naturally present in the production process, thereby increasing the corrosion resistance for temperatures below 850-950 ° C.
  • the quantity ratio of chromium to aluminum is limited to 3.6 to 6.5 in order to prevent the formation of brittle ß phases.
  • the quantity ratio of nickel to chromium is limited to 2.3 to 3.0 in order to prevent brittle ⁇ phases, which improves the resistance to temperature changes.
  • the firm and permanent adhesion of the protective layer and its cover layer with frequent changes in temperature is achieved by the percentage of yttrium specifically determined for the alloy.
  • composition chosen here shows no or only small proportions by volume of ⁇ -phase or ß-NiAI-phase (FIG. 1), so that significant advantages can be expected under thermal cycling.
  • the comparative alloy from FIG. 2 shows a similar composition for some elements, but due to the differences in other elements, a very different microstructure is shown, which, based on our experience, will not have sufficient resistance to thermal shock for turbines and also due to the beginning melting above 900 ° C cannot be used.
  • the production-related, inherent contamination of sulfur which can typically reach a concentration of less than 10 ppm, but in some cases up to 50ppm, leads to reduced resistance to oxidation and corrosion.
  • the trace elements Mg and Ca which absorb sulfur, are added during the production of the coating.
  • the alloy is applied directly to the base material of the component or to an intermediate layer consisting of a third composition.
  • the layer thicknesses vary between 0.03 mm and 1.5 mm.
  • Fig. 1 shows the phase balance (molar fraction ⁇ [%] vs. temperature [ 9 C]) according to the composition given here
  • Fig. 2 shows the phase balance (molar fraction ⁇ [%] vs. temperature [ Q C]) according to that in the US patent -A-4,973,445 specified composition.
  • the invention is explained in more detail using an exemplary embodiment which describes the production of a coated gas turbine component or another component of a thermal turbomachine.
  • the gas turbine component to be coated is made of an austenitic material, in particular a nickel superalloy. Before coating, the component is first chemically cleaned and then roughened using a blasting process. The component is coated under vacuum, under protective gas or in air by means of thermal spray processes (LPPS, VPS, APS), high-speed spraying (HVOF), electrochemical processes, physical / chemical evaporation (PVD, CVD) or another known from the prior art coating process.
  • LPPS thermal spray processes
  • VPS high-speed spraying
  • PVD physical / chemical evaporation
  • CVD chemical evaporation
  • a NiCrAlY alloy is used for the coating, which according to the invention (% by weight) contains 23 to 27% by weight chromium, 4 to 7% by weight aluminum, 0.1 to 3% by weight silicon, 0.1 to 3% by weight. % Tantalum, 0.2 to 2% by weight yttrium, 0.001 to 0.01% by weight boron, 0.001 to 0.01% by weight magnesium and 0.001 to 0.01% by weight calcium.
  • the rest of the alloy consists of nickel and unavoidable impurities.
  • the Al content is preferably in a range from over 5 to 6% by weight. All weights refer to the total weight of the alloy used.
  • the alloy according to the invention has a significant improvement in the oxidation and corrosion resistance compared to the already known high-temperature protective layers.
  • the high-temperature protective layer according to the invention it can be established that it is at high temperatures (depending on the design above 800 ° C) has aluminum-containing ⁇ and ⁇ ' phases with a volume fraction of at least 50%, which enables the formation of an aluminum oxide-containing protective layer, at low and at medium temperatures (depending on the version below 900 ° C) chromium-containing ⁇ -Cr phases of more than 5%, which enables the formation of a protective layer containing chromium oxide.
  • the composition selected here shows no or only small proportions by volume of ⁇ -phase or ⁇ -NiAI phase or boride phases (referred to in FIG. 1 as M2B_ORTH), so that there are clear advantages under thermal cycling are to be expected.
  • the comparative alloy (Fig. 2) shows a similar composition for some elements, but due to the differences in other elements, a very different microstructure is shown which, based on our experience, will not have sufficient resistance to temperature changes for turbines and also due to the beginning melting above 900 ° C cannot be used.
  • silicon and boron are added to the base material that forms the high temperature protective layer. This significantly increases the protection of the high-temperature protective layer and the component located underneath.
  • the production-related, inherent contamination of sulfur which can typically reach a concentration of less than 10 ppm, but in some cases also 50 ppm, leads to reduced oxidation and corrosion resistance.
  • the Spu 'renetti Mg and Ca added in the preparation of the coating to absorb the sulfur and thereby increases in temperatures below 850 to 950 ° C the corrosion resistance.
  • the quantity ratio of chromium to aluminum is limited to 3.6 to 6.5 in order to prevent the formation of brittle ß phases.
  • the quantity ratio of nickel to chromium is limited to 2.3 to 3.0 to prevent brittle ⁇ phases, which improves the resistance to temperature changes.
  • the firm and permanent adhesion of the protective layer and its cover layer with frequent changes in temperature is achieved by the percentage of yttrium specifically determined for the alloy.
  • the material forming the alloy is in powder form for the thermal spraying processes and preferably has a grain size of 5 to 90 ⁇ m.
  • the alloy is produced 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. Depending on the coating process, the layer thicknesses vary between 0.03 mm and 1.5 mm.
  • the component is subjected to a heat treatment. This takes place at a temperature of 1000 to 1200 ° C. for about 10 minutes 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)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Inorganic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Ceramic Products (AREA)
  • Resistance Heating (AREA)
  • Organic Insulating Materials (AREA)
  • Magnetic Heads (AREA)
  • Physical Vapour Deposition (AREA)
  • Spark Plugs (AREA)
EP03700010A 2002-01-18 2003-01-16 Revetement de protection haute temperature Expired - Lifetime EP1466037B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10202012 2002-01-18
DE10202012 2002-01-18
PCT/CH2003/000023 WO2003060194A1 (fr) 2002-01-18 2003-01-16 Revetement de protection haute temperature

Publications (2)

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

Family

ID=7712588

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03700010A Expired - Lifetime EP1466037B1 (fr) 2002-01-18 2003-01-16 Revetement de protection haute temperature

Country Status (12)

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

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 (fr) 2007-06-25 2014-07-23 Sulzer Metaplas GmbH Système de couche destiné à la formation d'une couche superficielle à la surface d'un substrat, tout comme source d'évaporation destinée à la fabrication d'un système de couche
WO2009109199A1 (fr) * 2008-03-04 2009-09-11 Siemens Aktiengesellschaft Alliage, couche protectrice contre la corrosion à haute température et système stratifié
DE102010021691A1 (de) * 2010-05-27 2011-12-01 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Schichtverbund mit einer eindimensionalen Kompositstruktur
EP2474413A1 (fr) * 2011-01-06 2012-07-11 Siemens Aktiengesellschaft Alliage, couche de protection et composant
US9359669B2 (en) * 2011-12-09 2016-06-07 United Technologies Corporation Method for improved cathodic arc coating process
EP3118345B1 (fr) 2015-07-17 2018-04-11 Ansaldo Energia IP UK Limited Revêtement protecteur à haute température
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
KR102711268B1 (ko) * 2019-03-07 2024-09-26 오를리콘 메트코 (유에스) 아이엔씨. 열 사이클 피로 내성 및 황화부식 저항성이 향상된 tbc용 고도의 접합 코트 재료
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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Also Published As

Publication number Publication date
WO2003060194A1 (fr) 2003-07-24
BR0306989B1 (pt) 2012-03-06
CA2473565A1 (fr) 2003-07-24
ATE299536T1 (de) 2005-07-15
US7052782B2 (en) 2006-05-30
BR0306989A (pt) 2004-12-14
JP4217626B2 (ja) 2009-02-04
ES2244914T3 (es) 2005-12-16
DE50300758D1 (de) 2005-08-18
CA2473565C (fr) 2010-12-07
EP1466037B1 (fr) 2005-07-13
RU2004125154A (ru) 2005-07-20
RU2301284C2 (ru) 2007-06-20
CN1617951A (zh) 2005-05-18
US20050042474A1 (en) 2005-02-24
CN100350075C (zh) 2007-11-21
JP2005514525A (ja) 2005-05-19
AU2003200835A1 (en) 2003-07-30

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