EP0592310B1 - Coating for parts rubbing by rotation of a martesitic steel article - Google Patents

Coating for parts rubbing by rotation of a martesitic steel article Download PDF

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Publication number
EP0592310B1
EP0592310B1 EP93402458A EP93402458A EP0592310B1 EP 0592310 B1 EP0592310 B1 EP 0592310B1 EP 93402458 A EP93402458 A EP 93402458A EP 93402458 A EP93402458 A EP 93402458A EP 0592310 B1 EP0592310 B1 EP 0592310B1
Authority
EP
European Patent Office
Prior art keywords
coating
rotation
cr3c2
grains
martesitic
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
EP93402458A
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German (de)
French (fr)
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EP0592310A1 (en
Inventor
André Coulon
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.)
Alstom SA
Original Assignee
GEC Alsthom Electromecanique SA
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Filing date
Publication date
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Publication of EP0592310A1 publication Critical patent/EP0592310A1/en
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Anticipated expiration legal-status Critical
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    • 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
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic

Definitions

  • the present invention relates to a surface coating on martensitic steel for parts rubbing by rotation.
  • Martensitic steels and particularly those containing 9 to 18% chromium have a high sensitivity to seizure. Comparative tests have shown such a difference in the friction behavior of these steels compared to ferritic steels that surface treatment is necessary, particularly when the mechanical part concerned is in rotation and rests on bearings or rests on a stop. The slightest lubrication fault can indeed lead to an almost instantaneous deterioration of the supporting bristles.
  • the coating according to the invention having a low coefficient of friction and good adhesion and easy to deposit is characterized in that it comprises a NiMo matrix in which grains of Cr3C2 are embedded. It is important that the matrix does not contain chromium as this weakens the matrix.
  • the grain of Cr3C2 are used to give hardness to the NiMo ductile matrix.
  • composition by weight of the coating is as follows: Cr3C2 15 to 25% Mo 15 to 25% Or 55 to 65%
  • the particle size of the MoNi matrix is 20 to 90 ⁇ m.
  • the Cr3C3 comprises 2% by weight of submicron grains. These grains are found mainly in the vicinity of the surface and play a protective role ensuring a form of dry lubrication.
  • Figure 1 shows the diagram of a device for depositing the coating according to the invention.
  • Figure 2 shows the coating according to the invention.
  • the torch 1 represented in FIG. 1 comprising a combustion chamber 2 supplied with a gaseous mixture comprising propane, oxygen with hydrogen and nitrogen and a central tube 3 supplied with a mixture of powders.
  • the gas mixture passes from chamber 2 into a conduit 4 surrounding the tube 3.
  • the end of the conduit 4 and the end of the tube 3 open to the outside where a flame 5 occurs.
  • the powder crosses the flame and is projected at high speed by the carrier gas.
  • the part to be coated (not shown) is placed at a short distance (200-400mm) from the torch and it moves in front of the part by an automatic advance system.
  • the preparation of the surfaces to be coated is known to those skilled in the art: degreasing followed by buckling, sandblasting in order to promote the mechanical attachment of the coating.
  • the thermal projection of the powder is carried out in a dynamic mode: rotor in rotation, torch moving horizontally for the bristles of the rotor, or vertically for the faces of the stop.
  • the optimum coating thickness is between 30 and 60 ⁇ m.
  • Powder is a specific alloy, particularly suitable for an application for turbine rotors.
  • the proportions of the powder mixture are as follows (in% of the weight). Cr3C2 20% ⁇ 5% Or 60% ⁇ 5% Mo 20% ⁇ 5%
  • the particle size of the powder must be chosen so that at least 90% by weight of the chromium carbide used is obtained from a submicron and spherical Cr3C2 then agglomerated and sintered to a size of 10 to 30 ⁇ m.
  • the particle size of the NiMo mixture will be from 20 ⁇ m to 90 ⁇ m.
  • the coating 6 of the part 7 (see FIG. 2) comprises large sintered grains 8 of Cr3C2 which ensure the hardness of the coating.
  • the NiMo matrix 9 made up of grains from 20 ⁇ m to 90 ⁇ m is ductile so that if there is a lubrication incident, the coating will reduce friction.
  • the coating comprises submicron grains 10 of Cr3C2, preferably 2% by weight of Cr3C2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Sliding-Contact Bearings (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Description

La présente invention concerne un revêtement de surface sur acier martensitique pour parties frottantes par rotation.The present invention relates to a surface coating on martensitic steel for parts rubbing by rotation.

Les aciers martensitiques et particulièrement ceux qui contiennent 9 à 18% de chrome ont une grande sensibilité au grippage. Des essais comparatifs ont mis en évidence une telle différence de comportement au frottement de ces aciers par rapport aux aciers ferritiques qu'un traitement de surface s'avère nécessaire particulièrement lorsque la pièce mécanique concernée est en rotation et repose sur des coussinets ou s'appuie sur une butée. Le moindre défaut de lubrification peut en effet entrainer une détérioration presque instantanée des soies porteuses.Martensitic steels and particularly those containing 9 to 18% chromium have a high sensitivity to seizure. Comparative tests have shown such a difference in the friction behavior of these steels compared to ferritic steels that surface treatment is necessary, particularly when the mechanical part concerned is in rotation and rests on bearings or rests on a stop. The slightest lubrication fault can indeed lead to an almost instantaneous deterioration of the supporting bristles.

Dans le cas d'un rotor de turbine en acier martensitique, ce traitement est impérieux et préviendra tout risque de grippage.In the case of a martensitic steel turbine rotor, this treatment is imperative and will prevent any risk of seizure.

Il est déjà connu de revêtir les surfaces frottantes de chrome mais le dépôt de ce revêtement est relativement onéreux et nécessite une installation spéciale.It is already known to coat rubbing surfaces with chromium, but depositing this coating is relatively expensive and requires special installation.

Le revêtement selon l'invention présentant un faible coefficient de frottement et une bonne adhérence et facile à déposer est caractérisé en ce qu'il comporte une matrice NiMo dans laquelle sont noyés des grains de Cr₃C₂. Il est important que la matrice ne comporte pas de chrome car cela fragilise la matrice.The coating according to the invention having a low coefficient of friction and good adhesion and easy to deposit is characterized in that it comprises a NiMo matrix in which grains of Cr₃C₂ are embedded. It is important that the matrix does not contain chromium as this weakens the matrix.

Le grain de Cr₃C₂ servent à donner de la dureté à la matrice ductile NiMo.The grain of Cr₃C₂ are used to give hardness to the NiMo ductile matrix.

De préférence la composition en poids du revêtement est la suivante: Cr₃C₂ 15 à 25% Mo 15 à 25% Ni 55 à 65% Preferably the composition by weight of the coating is as follows: Cr₃C₂ 15 to 25% Mo 15 to 25% Or 55 to 65%

La granulométrie de la matrice MoNi est de 20 à 90 µm.The particle size of the MoNi matrix is 20 to 90 μm.

Selon un perfectionnement intéressant de l'invention le Cr₃C₂ comporte 2% en poids de grains submicroniques. Ces grains se retrouvent en majeure partie au voisinage de la surface et jouent un rôle protecteur assurant une forme de graissage sec.According to an interesting improvement of the invention, the Cr₃C₃ comprises 2% by weight of submicron grains. These grains are found mainly in the vicinity of the surface and play a protective role ensuring a form of dry lubrication.

L'invention va maintenant être décrite plus en détail en se référant à un mode de réalisation particulier cité à titre d'exemple non limitatif et représenté par les dessins annexés.The invention will now be described in more detail with reference to a particular embodiment cited by way of nonlimiting example and represented by the accompanying drawings.

La figure 1 représente le schéma d'un dispositif pour déposer le revêtement selon l'invention.Figure 1 shows the diagram of a device for depositing the coating according to the invention.

La figure 2 représente le revêtement selon l'invention.Figure 2 shows the coating according to the invention.

La torche 1 représentée à la figure 1 comportant une chambre de combustion 2 alimentée en un mélange gazeux comportant du propane de l'oxygène de l'hydrogène et de l'azote et un tube central 3 alimenté en mélange de poudres.The torch 1 represented in FIG. 1 comprising a combustion chamber 2 supplied with a gaseous mixture comprising propane, oxygen with hydrogen and nitrogen and a central tube 3 supplied with a mixture of powders.

Le mélange gazeux passe de la chambre 2 dans un conduit 4 entourant le tube 3.The gas mixture passes from chamber 2 into a conduit 4 surrounding the tube 3.

L'extrémité du conduit 4 et l'extrémité du tube 3 débouchent à l'extérieur ou se produit une flamme 5. La poudre traverse la flamme et est projetée à grande vitesse par le gaz porteur.The end of the conduit 4 and the end of the tube 3 open to the outside where a flame 5 occurs. The powder crosses the flame and is projected at high speed by the carrier gas.

La pièce a revêtir (non représentée) est disposée à faible distance (200-400mm) de la torche et celle-ci se déplace devant la pièce par un système automatique d'avance.The part to be coated (not shown) is placed at a short distance (200-400mm) from the torch and it moves in front of the part by an automatic advance system.

Dans l'application à un rotor de turbine, celui-ci est monté sur un tour horizontal, et est entraîné à une faible vitesse de rotation.In the application to a turbine rotor, this is mounted on a horizontal lathe, and is driven at a low speed of rotation.

La préparation des surfaces à revêtir est connue de l'homme de l'art: dégraissage suivi de flambage, sablage en vue de favoriser l'accrochage mécanique du revêtement.The preparation of the surfaces to be coated is known to those skilled in the art: degreasing followed by buckling, sandblasting in order to promote the mechanical attachment of the coating.

La projection thermique de la poudre est réalisée selon un mode dynamique: rotor en rotation, torche se déplaçant horizontalement pour les soies du rotor, ou verticalement pour les faces de la butée. L'épaisseur optimale du revêtement est comprise entre 30 et 60 µm.The thermal projection of the powder is carried out in a dynamic mode: rotor in rotation, torch moving horizontally for the bristles of the rotor, or vertically for the faces of the stop. The optimum coating thickness is between 30 and 60 µm.

La poudre est un alliage spécifique, particulièrement adapté à une application pour des rotors de turbine.Powder is a specific alloy, particularly suitable for an application for turbine rotors.

Les proportions au mélange de poudres sont les suivants (en % du poids). Cr₃C₂ 20% ± 5% Ni 60% ± 5% Mo 20% ± 5% The proportions of the powder mixture are as follows (in% of the weight). Cr₃C₂ 20% ± 5% Or 60% ± 5% Mo 20% ± 5%

La granulométrie de la poudre doit être choisie pour qu'au moins 90% en poids du carbure de chrome utilisé soit obtenu à partir d'un Cr₃C₂ submicronique et sphérique puis aggloméré et fritté à une taille de 10 à 30 µm.The particle size of the powder must be chosen so that at least 90% by weight of the chromium carbide used is obtained from a submicron and spherical Cr₃C₂ then agglomerated and sintered to a size of 10 to 30 μm.

La granulométrie du mélange NiMo sera de 20 µm à 90 µm.The particle size of the NiMo mixture will be from 20 µm to 90 µm.

Le revêtement 6 de la pièce 7 (voir figure 2) comporte des gros grains frittés 8 de Cr₃C₂ qui assurent la dureté du revêtement. La matrice 9 de NiMo constitués de grains de 20µm à 90µm est ductile si bien que s'il y a un incident de graissage le revêtement réduira le frottement. De plus selon une réalisation préférentielle de l'invention le revêtement comporte des grains submicroniques 10 de Cr₃C₂ de préférence 2% en poids du Cr₃C₂.The coating 6 of the part 7 (see FIG. 2) comprises large sintered grains 8 of Cr₃C₂ which ensure the hardness of the coating. The NiMo matrix 9 made up of grains from 20 μm to 90 μm is ductile so that if there is a lubrication incident, the coating will reduce friction. In addition, according to a preferred embodiment of the invention, the coating comprises submicron grains 10 of Cr₃C₂, preferably 2% by weight of Cr₃C₂.

Ces grains 10 jouent un rôle protecteur assurant une forme de graissage "sec" au voisinage des surfaces de contacts en rotation (arbre-coussinet).These grains 10 play a protective role ensuring a form of "dry" lubrication in the vicinity of the rotating contact surfaces (shaft-bearing).

Claims (4)

  1. A surface coating on martensitic steel for portions that rub by rotation, characterized in that it comprises a matrix (9) of NiMo in which grains of Cr₃C₂ are embedded, 90% by weight of which are constituted by grains in the range 10 µm to 30 µm.
  2. A coating according to claim 2, characterized in that it has the following composition by weight: Cr₃C₂ 15% to 25%; Mo 15% to 25%; Ni 55% to 65%.
  3. A coating according to claim 2, characterized in that the grain size of the NiMo matrix (9) is 20 µm to 90 µm.
  4. A coating according to any preceding claim, characterized in that about 2% by weight of the Cr₃C₂ is constituted submicron grains (10) with the major portion thereof being close to the surface of the coating (6).
EP93402458A 1992-10-09 1993-10-06 Coating for parts rubbing by rotation of a martesitic steel article Expired - Lifetime EP0592310B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9212021 1992-10-09
FR9212021A FR2696760B1 (en) 1992-10-09 1992-10-09 Coating for rubbing parts by rotation of a piece of matensitic steel.

Publications (2)

Publication Number Publication Date
EP0592310A1 EP0592310A1 (en) 1994-04-13
EP0592310B1 true EP0592310B1 (en) 1995-09-06

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EP93402458A Expired - Lifetime EP0592310B1 (en) 1992-10-09 1993-10-06 Coating for parts rubbing by rotation of a martesitic steel article

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US (1) US5449562A (en)
EP (1) EP0592310B1 (en)
JP (1) JPH06212448A (en)
DE (1) DE69300449T2 (en)
FR (1) FR2696760B1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW383233B (en) * 1995-01-31 2000-03-01 Rieter Ag Maschf Thread guiding elements
JPH0931628A (en) * 1995-07-25 1997-02-04 Riken Corp Sliding member and its production
US7479630B2 (en) * 2004-03-25 2009-01-20 Bandura Dmitry R Method and apparatus for flow cytometry linked with elemental analysis
US20050241896A1 (en) * 2004-04-28 2005-11-03 Gerald Martino Brake rotors with heat-resistant ceramic coatings
GB0821459D0 (en) 2008-11-24 2008-12-31 Icera Inc Active power management
US8906130B2 (en) 2010-04-19 2014-12-09 Praxair S.T. Technology, Inc. Coatings and powders, methods of making same, and uses thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US3941903A (en) * 1972-11-17 1976-03-02 Union Carbide Corporation Wear-resistant bearing material and a process for making it
ES445000A1 (en) * 1975-02-10 1977-07-16 Union Carbide Corp Two layer coating system
US4173457A (en) * 1978-03-23 1979-11-06 Alloys, Incorporated Hardfacing composition of nickel-bonded sintered chromium carbide particles and tools hardfaced thereof
US4275124A (en) * 1978-10-10 1981-06-23 United Technologies Corporation Carbon bearing MCrAlY coating
US4290510A (en) * 1978-12-14 1981-09-22 Chrysler Corporation Wear resistant coated article
US4334927A (en) * 1980-12-08 1982-06-15 Hyde Glenn F Piston ring coatings
EP0108877B1 (en) * 1982-09-16 1988-08-03 Rabewerk Heinrich Clausing Method of applying protective coatings to the surfaces of tools and devices
JPS6033364A (en) * 1983-08-01 1985-02-20 Koei Seikou Kk Hearth roll for heat treating furnace and preparation thereof
FR2563540B1 (en) * 1984-04-26 1989-05-05 Alsthom Atlantique DEVICE FOR CARRYING OUT A METAL DEPOSIT ON THE FRICTING PARTS OF A TURBINE ROTOR
GB8414219D0 (en) * 1984-06-04 1984-07-11 Sherritt Gordon Mines Ltd Production of nickel-chromium/carbide coating on substrates
DE3515107C1 (en) * 1985-04-26 1986-07-31 Goetze Ag, 5093 Burscheid Spray powder for the production of wear-resistant and escape-proof coatings
US4731253A (en) * 1987-05-04 1988-03-15 Wall Colmonoy Corporation Wear resistant coating and process
FR2638781B1 (en) * 1988-11-09 1990-12-21 Snecma ELECTROPHORETIC ANTI-WEAR DEPOSITION OF THE CONSOLIDATED METALLOCERAMIC TYPE BY ELECTROLYTIC NICKELING
US5137422A (en) * 1990-10-18 1992-08-11 Union Carbide Coatings Service Technology Corporation Process for producing chromium carbide-nickel base age hardenable alloy coatings and coated articles so produced

Also Published As

Publication number Publication date
FR2696760A1 (en) 1994-04-15
DE69300449D1 (en) 1995-10-12
DE69300449T2 (en) 1996-02-22
FR2696760B1 (en) 1994-11-04
EP0592310A1 (en) 1994-04-13
US5449562A (en) 1995-09-12
JPH06212448A (en) 1994-08-02

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