EP0219536B1 - Couche de protection - Google Patents

Couche de protection Download PDF

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Publication number
EP0219536B1
EP0219536B1 EP86902820A EP86902820A EP0219536B1 EP 0219536 B1 EP0219536 B1 EP 0219536B1 EP 86902820 A EP86902820 A EP 86902820A EP 86902820 A EP86902820 A EP 86902820A EP 0219536 B1 EP0219536 B1 EP 0219536B1
Authority
EP
European Patent Office
Prior art keywords
coating
layer
carrier
tib2
protective
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
EP86902820A
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German (de)
English (en)
Other versions
EP0219536A1 (fr
Inventor
Heiko Gruner
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.)
Plasmainvent AG
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Plasmainvent 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 Plasmainvent AG filed Critical Plasmainvent AG
Priority to AT86902820T priority Critical patent/ATE68019T1/de
Publication of EP0219536A1 publication Critical patent/EP0219536A1/fr
Application granted granted Critical
Publication of EP0219536B1 publication Critical patent/EP0219536B1/fr
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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • Y10T428/12458—All metal or with adjacent metals having composition, density, or hardness gradient
    • 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
    • Y10T428/12576—Boride, carbide or nitride 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.]
    • Y10T428/12639—Adjacent, identical composition, components
    • Y10T428/12646—Group VIII or IB metal-base
    • 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
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component

Definitions

  • the invention relates to a protective layer applied in a plasma spraying process to a metallic carrier, consisting of at least one metallic adhesive layer and a multilayer top layer which has different proportions of metallic and ceramic materials in its layers.
  • Protective layers of this type can be applied to very different carrier bodies. The intention is always associated with increasing the service life of the carrier body in a specific application and / or opening up new areas of use for the carrier material. With the help of the protective layer, workpiece surfaces can be given specific properties at specific points. This extends the possible uses of the workpieces and increases their resistance in daily use.
  • the PCT-WO-82/01898 protective layers of the type described have become known, which have an adhesive layer of NiCrAlY and a multilayer top layer with different layers of oxide ceramic materials such as ZrO2-Y2O3, Al2O3 or Ca2SiO4.
  • the total layer thickness given there on the examples is between 0.8 mm and 2.5 mm, according to the claims there 0.5 to 8 mm or 2 to 7 mm.
  • the adhesive layer thickness there is 0.1 mm, 0.15 mm or 0.2 mm.
  • VPS technique The vacuum plasma spraying technique was developed from these points of view. Their development, taking into account the special requirements of this new technology, led to significant improvements in coating conditions and layer properties compared to spraying in the atmosphere. Vacuum plasma spraying is a further development and addition to the atmospheric plasma spraying process (APS process). It differs from this principle in that the coating process takes place in a vacuum chamber at negative pressure.
  • the workpiece surface can be cleaned in a sputtering process before coating. Gas contamination, water vapor and oxide layers are dusted off. This leads to a significant improvement in the adhesion of the spray layers, especially on smooth surfaces.
  • free surface energy of cleaned carriers is saturated by layer atoms.
  • favorable conditions are created for interdiffusion processes between the carrier material and the layer.
  • the coating process is carried out in a vacuum, all substrates can be heated to their thermal stability limit before coating.
  • the heating effect of the plasma flame can be increased with the help of the transmitted arc. Targeted temperature changes during or after coating are possible without the risk of oxidation for the substrate and layer. This avoids or reduces internal stresses in the spray layer.
  • Oxide-free layers are formed which have the same chemical composition as the wettable powder. Responsive powders find no reactant, their melting temperature and heat of fusion are not affected.
  • vacuum plasma spray layers examples include Protection against hot corrosion, oxidation and erosion of turbine components, Electrical insulation and / or thermal insulation, Chemical resistance and Radiation protection in nuclear technology.
  • the invention has for its object to provide a protective layer of the type described in the introduction, which can be used practically universally in all four main areas of application of the plasma spray layers, in particular effectively protecting the carrier at the same time against corrosion, oxidation, erosion, chemical attack and radiation, him electrically insulated and temporarily protected from overheating by thermal insulation.
  • the intermediate layer consists of a mixture of the materials of the adhesive layer and the cover layer, provides a particularly good connection between the tightly sprayed adhesive layer and the closely sprayed cover layer, the different thermal expansion coefficients of which are matched to one another.
  • the intermediate layer is expediently constructed with a continuously graded transition from the material of the adhesive layer to the material of the cover layer.
  • the intermediate layer is advantageously sprayed on starting with the spray chamber pressure when the adhesive layer is applied and gradually progressing to the spray chamber pressure when the cover layer is applied.
  • the adhesive layer can advantageously have a thickness of approximately 200 ⁇ m, the intermediate layer a thickness of up to 5 mm and the cover layer a thickness of up to 500 ⁇ m.
  • the protective layer effect is given by the tightness of the cover layer, which for refractory materials with very high melting temperatures can practically only be achieved with the VPS method at these layer thicknesses. It is thus possible to combine materials with very different physical properties in a stable and temperature-resistant manner, without the protective layer coming off, cracking and thus losing its protective effect in the various areas of use.
  • the grain size of the wettable powder is advantageously a maximum of 25 microns, so that it is ensured that both when spraying the adhesive layer with the top layer, but especially when spraying the intermediate layer, all wettable powder particles form the spray layer as molten droplets. This and in conjunction with the high mechanical impact energy ensures the tightness of the spray layer.
  • An essential feature of the protective layer structure is the lamellar overlap of the materials of the adhesive layer and the cover layer in the intermediate layer, which is caused by the liquid spray powder particles bursting apart on impact on the workpiece surface.
  • the protective layer produced according to the invention only develops its effect when its density practically corresponds to the solid value.
  • the material of the carrier and the adhesive layer can advantageously be made of Ti and the material of the intermediate layer can be made of 80% Ti and There are 20% TiB2, the material of the cover layer being TiB2.
  • the material of the carrier and the adhesive layer can consist of a superalloy and the material of the intermediate layer can consist of 100% superalloy with graded transition into 100% TiB2.
  • the material of the carrier can advantageously also consist of a superalloy and the material of the adhesive layer can consist of an alloy of the type M-CrAlY which is matched to the alloy of the carrier, where M is Fe, Co, Ni or NiCo as the main alloy component.
  • the material of the intermediate layer consists of 100% M-CrAlY graded in 100% TiB2. In 738 is advantageously used as a superalloy.
  • the material of the carrier and the adhesive layer can advantageously be made of steel and the material of the intermediate layer can consist of 50% steel and 50% TiB2.
  • the carrier 1 shows a carrier 1 which has been degassed on its surface 2 prior to the application of a composite protective layer 3, 4, 5 and has been heated to a certain temperature.
  • the surface 2 of the carrier 1 can be specially treated, for example roughened by sandblasting, and sputter-cleaned prior to coating with the aid of the transferred arc and freed from absorbed gases, water and thin oxide layers.
  • an adhesive layer 3 is applied using the VPS method, the chemical composition of which largely corresponds to the material of the carrier 1 and has practically the same thermal expansion coefficient as the carrier 1.
  • the cover of the adhesive layer 3 is preferably approx. 50 ⁇ m, but can also be any larger if e.g. in the event of a repair, a worn surface should be returned to its original dimension.
  • an intermediate layer 4 is applied, and on this intermediate layer 4, a densely sprayed cover layer 5 with a preferred thickness of 50 to 100 microns made of TiB2 is applied. Both the intermediate layer 4 and the cover layer 5 are also deposited using the VPS method.
  • the intermediate layer 4 consists of a mixture of the materials of the adhesive layer 3 and the cover layer 5 and is formed, for example, with a graded transition between the latter two layers.
  • the cover layer 5 made of TiB2 represents the actual protective layer of the composite protective layer 3, 4, 5, which corresponds to the solid material as far as possible in its layer structure, that is to say is as dense as possible, in contrast to previously known layers of refractory material, that is to say has no residual porosity and no microporosity. and built in macro cracks.
  • a turbine component that consists of a titanium alloy for reasons of weight and mechanical properties is exposed to severe erosion loads in practical operation.
  • a protective layer according to the invention consisting of a Ti adhesive layer 3, an intermediate layer 4, produced by simultaneous powder injection of 80% Ti and 20% TiB2, and a pure TiB2 cover layer 5, it is possible to reduce the erosion attack very strongly.
  • the adhesive layer 3 is approximately 20 to 50 ⁇ m thick, the intermediate layer 4 advantageously approximately 20 to 50 ⁇ m and the cover layer 5 on average 40 ⁇ m.
  • the coating is designed so that at the particularly erosive forces exposed to gas entry points such as the leading edge or the pressure side of a turbine blade, the thickness of the TiB2 cover layer 5 was specifically increased to about 50 microns.
  • TiB2 cover layer 5 with a layer hardness above 2300, measured according to the Vickers method, has a very low erosion rate, while according to the prior art, rather softer materials have a high erosion stability.
  • a carrier 1 made of a superalloy e.g. In 738
  • these types of material are subjected to a specific heat treatment to produce a material structure that only has the mechanical high-temperature properties. This heat treatment takes place at temperatures where intermetallic diffusion can take place. It is therefore particularly advantageous to coat this carrier 1 with an adhesive layer 3 of the same material composition, since this prevents the depletion and enrichment of alloy components in the adhesive layer 3 and in the carrier 1, which is always associated with changes in the mechanical properties, that should be avoided.
  • the preferred protective layer structure in this application is adhesive layer 3 In 738 about 100 ⁇ m thick, graded transition from 100% In 738 to 100% TiB2 in the intermediate layer 4 to a layer thickness of approximately 200 ⁇ m, and top layer 5 TiB2 approximately 50 ⁇ m thick with targeted reinforcements to 80 ⁇ m at the critical points.
  • an alloy material of the type M-CrAlY which is matched to the carrier material can advantageously be used for the adhesive layer 3, M Fe, Co, Ni and NiCo being used as the main alloy component.
  • the preferred wettable powder granulation is limited to a maximum of 25 ⁇ m in order to produce a uniform gradation transition with a material distribution that is as homogeneous as possible and to spray the top layer 5 tightly.
  • a support 1 made of steel is to be used as an aluminum die-casting tool and is to be protected against the attack of liquid Al.
  • spray powder of this type of steel is used for the adhesive layer 3, the thickness of the adhesive layer 3 preferably being up to 200 ⁇ m.
  • the thickness of the intermediate layer 4 made of a 50:50 mixture of steel spray powder and TiB2 is relatively small at 50 ⁇ m. Since the temperature for liquid aluminum is around 700 ° C, the TiB2 cover layer is 5 100 ⁇ m thick. Since die casting tools have a perfect fit, the total layer application on the workpiece must be taken into account before coating.
  • a protective layer is sought for the first wall boundary of the fusion plasma, which protects the carrier material against ion bombardment and electrical flashovers with a high current density, but is temperature-resistant in an inert gas atmosphere, has a low sputtering rate under particle bombardment and meets the requirement for the lowest possible atomic number.
  • TiB2 has proven itself for the top layer 5, the temperature resistance of which is 3200 ° C. in a vacuum.
  • the protective layer structure depends on the selected carrier material and is otherwise composed according to the invention.
  • Components of hydropower plants are particularly exposed to erosive forces, which are further reinforced by the effect of cavitation.
  • a substantial material reserve is usually included in order to achieve a certain service life despite severe erosion.
  • a protective layer in this application should also be able to be applied correspondingly thickly.
  • the protective layer according to the invention also develops an ideal protective effect here.
  • adhesive layer material can first be sprayed on until the original configuration of the component is reached again, and then the protective layer 3, 4 , 5 to be reapplied with the tried and tested layer structure.

Claims (6)

  1. Couche de protection (3, 4, 5) sur un support métallique (1), déposée selon un procédé de projection au plasma sous vide, composée d'au moins une couche adhésive (3) métallique et d'une surface multicouches présentant dans ses couches des pourcentages divers de matériaux métalliques et céramiques, caractérisée en ce que dans la couche de protection, à la couche adhésive fait suite une couche intermédiaire surmontée d'une couche de recouvrement,
    (a) la couche de protection (3, 4, 5) projetée dense étant déposée en l'absence de fissures ou de pores,
    (b) la couche adhésive (3) étant constituée par une couche projetée dense et ayant une composition chimique et un coefficient de dilatation thermique coïncidant sensiblement avec ceux du matériau support,
    (c) la couche intermédiaire (4) étant constituée par une couche projetée dense, nettement lamellaire, par mélange des matériaux de la couche adhésive (3) et de la couche de recouvrement (5),
    (d) la couche de recouvrement (5) étant constituée par du TiB₂ projeté dense,
    et l'épaisseur de la couche adhésive (3) étant de l'ordre de 20 à 200 µm, l'épaisseur de la couche intermédiaire (4) étant comprise entre 20 et 5 000 µm et l'épaisseur de la couche de recouvrement (5) étant de 30 à 500 µm.
  2. Couche de protection selon la revendication 1, caractérisée en ce que le matériau du support (1) et de la couche adhésive (3) est Ti et que le matériau de la couche intermédiaire (4) se compose de 80 % de Ti et de 20 % de TiB₂.
  3. Couche de protection selon la revendication 1, caractérisée en ce que le matériau du support (1) et de la couche adhésive (3) est un superalliage et que le matériau de la couche intermédiaire (4) se compose de 100 % de superalliage passant graduellement à 100 % de TiB₂.
  4. Couche de protection selon la revendication 1, caractérisée en ce que le matériau du support (1) est un superalliage et que le matériau de la couche adhésive (3) est un alliage de type M-CrAlY adapté à l'alliage du support (1), M, principal composant de l'alliage, étant Fe, Co, Ni ou NiCo et que le matériau de la couche intermédiaire (4) se compose de 100 % de M-CrAlY passant graduellement à 100 % de TiB₂.
  5. Couche de protection selon la revendication 4, caractérisée en ce que le superalliage est In 738.
  6. Couche de protection selon la revendication 1, caractérisée en ce que le matériau du support (1) et de la couche adhésive (3) est de l'acier et que le matériau de la couche intermédiaire (4) se compose de 50 % d'acier et de 50 % de TiB₂.
EP86902820A 1985-04-17 1986-04-17 Couche de protection Expired - Lifetime EP0219536B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86902820T ATE68019T1 (de) 1985-04-17 1986-04-17 Schutzschicht.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853513882 DE3513882A1 (de) 1985-04-17 1985-04-17 Schutzschicht
DE3513882 1985-04-17

Publications (2)

Publication Number Publication Date
EP0219536A1 EP0219536A1 (fr) 1987-04-29
EP0219536B1 true EP0219536B1 (fr) 1991-10-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86902820A Expired - Lifetime EP0219536B1 (fr) 1985-04-17 1986-04-17 Couche de protection

Country Status (6)

Country Link
US (1) US4808487A (fr)
EP (1) EP0219536B1 (fr)
JP (1) JPS62502974A (fr)
AT (1) ATE68019T1 (fr)
DE (2) DE3513882A1 (fr)
WO (1) WO1986006106A1 (fr)

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DE19625274A1 (de) * 1996-06-25 1998-01-02 Lwk Plasmakeramik Gmbh & Co Kg Verstärkung von thermisch gespritzten Hochtemperatur-Keramikformteilen mit thermisch gespritzten Metallschichten
CN103849834A (zh) * 2014-02-20 2014-06-11 西工大常熟研究院有限公司 基于二硼化钛的复合刀具涂层及其制备方法

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US4808487A (en) 1989-02-28
ATE68019T1 (de) 1991-10-15
WO1986006106A1 (fr) 1986-10-23
DE3681778D1 (de) 1991-11-07
JPS62502974A (ja) 1987-11-26
DE3513882A1 (de) 1986-10-23
EP0219536A1 (fr) 1987-04-29

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