EP1061153A1 - Sliding part coated with triboactive oxides having a deficiency of metal cations - Google Patents

Sliding part coated with triboactive oxides having a deficiency of metal cations Download PDF

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Publication number
EP1061153A1
EP1061153A1 EP00401715A EP00401715A EP1061153A1 EP 1061153 A1 EP1061153 A1 EP 1061153A1 EP 00401715 A EP00401715 A EP 00401715A EP 00401715 A EP00401715 A EP 00401715A EP 1061153 A1 EP1061153 A1 EP 1061153A1
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EP
European Patent Office
Prior art keywords
friction part
mechanical friction
part according
metal oxide
metal
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EP00401715A
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German (de)
French (fr)
Inventor
Tom Linnemann
Gérard Desplanches
Bernard Criqui
Mathias Woydt
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Renault SAS
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Renault SAS
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Publication of EP1061153A1 publication Critical patent/EP1061153A1/en
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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
    • 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
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/02—Light metals
    • F05C2201/021—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2203/00—Non-metallic inorganic materials
    • F05C2203/04—Phosphor

Definitions

  • the present invention relates to mechanical friction parts for internal combustion engines lubricated by a fluid, bearing a anti-wear coating based on specific metal oxides with a stoichiometric defect in metal cations.
  • the Applicant has discovered the surprising fact that a group of materials rarely used in mechanical engineering due to important creep phenomena, had very lubricating properties interesting when used as a solid lubricant applied on the surface of the mechanical friction parts of the engine.
  • These new triboactive materials are metallic oxides individuals with a weak defect in metal cations compared to to the stoichiometry of the mother oxide.
  • triboactive coatings applied to the surface of mechanical friction parts (homogeneous layer), either in the form of triboactive particles dispersed in a layer metallic or ceramic on the surface of mechanical friction parts (composite layer).
  • the object of the present invention is therefore a part friction mechanics for coated internal combustion engines, on a part or all of its surface, of a layer comprising at least a metal oxide having a stoichiometric cation defect metallic.
  • the invention also relates to manufacturing methods of a mechanical friction part for internal combustion engines coated, on part or all of its surface, with a layer comprising at least one metal oxide having a stoichiometric defect of metal cations.
  • the metal oxides having a stoichiometric defect in metal cations which can be used according to the present invention are chosen in particular from the following: Ni 1-y O, Co 1-y O, Cr 2-y O. Fe 1-y O, Fe 3-y O 4 Mn 1-y O where 10 -5 ⁇ y ⁇ 0.15.
  • the value of y determines the amount of creep and therefore the anti-wear properties of these oxides.
  • the appearance of gaps of metal ions in the crystal lattice of the oxide decreases by several orders of magnitude the creep stress and greatly improves its anti-wear properties.
  • the preferred ranges for y vary according to the different metal oxides. These preferred ranges are in particular the following: 10 -4 ⁇ y ⁇ 10 -2 for Ni 1-y O, Co 1-y O and Cr 2-y O 10 -3 ⁇ y ⁇ 0.15 for Fe 1-y O, 10 -3 ⁇ y ⁇ 0.03 for Fe 3-y O 4 , 10 -5 ⁇ y ⁇ 0.1 for Mn 1-y O
  • the thickness of the layer of triboactive material depends on the nature and architecture of the coating and the deposition process chosen and it will be adjusted according to the tribological constraints to which submitted the piece.
  • the thickness of this coating is generally between 5 ⁇ m and 1000 ⁇ m, and preferably between 10 ⁇ m and 200 ⁇ m, at operational status.
  • the thickness of this matrix containing triboactive particles is included between 5 ⁇ m and 1000 ⁇ m, and preferably between 10 ⁇ m and 100 ⁇ m, at operational status.
  • the matrix of the tri-boactive composite layer of the present invention may be a metallic or ceramic matrix.
  • metallic matrices examples include iron, nickel, nickel-phosphorus, chromium, cobalt, tungsten, molybdenum, an alloy of these metals, or cast iron and aluminum, brass (CuZn) or bronze (CuSn).
  • Ceramic matrices which can be used for the composite coatings according to the present invention are for example based on Al 2 O 3 , ZrO 2 , Cr 2 O 3 , TiO 2 or a mixture of these.
  • the average size of triboactive metal oxide particles presenting a stoichiometric defect in metallic cations used according to the present invention is generally between 0.3 and 30 ⁇ m, preferably between 0.5 and 5 ⁇ m.
  • the metallic or ceramic matrix are present in the metallic or ceramic matrix to from 5% to 70% by weight, preferably from 10% to 40% by weight relative to the total weight of the composite layer (matrix + particles). For a content of less than 5%, the anti-wear effectiveness of the coating is insufficient. Above 70% by weight, there are, for the most part ceramic and metallic matrices, a risk of lack of cohesion and / or adhesion of the composite layer.
  • triboactive coatings of the present invention are suitable only for mechanical friction parts submitted, in the motor, to sliding constraints.
  • lifters, camshaft cams, piston pins, segments, liners, valve guides, valve stems, timing rings and gears oil pump we can mention in particular the lifters, camshaft cams, piston pins, segments, liners, valve guides, valve stems, timing rings and gears oil pump.
  • Anti-wear coatings based on metal oxides with a stoichiometric defect in cations can be deposited on the surface mechanical parts by thermal spraying or by galvanic deposition.
  • a fine powder of metal oxide having a stoichiometric cation defect metallic or a mixture of such a powder with a powder forming the matrix of the composite coating, namely a metallic powder or a ceramic powder.
  • Galvanic deposition is especially suitable for composite coatings with metallic matrix in nickel, nickel-phosphorus or chromium.

Abstract

The friction part is coated on part or on the whole of its surface with a layer comprising at least a metal oxide having a stoichiometric deficiency of metal cations and selected from Co1-yO, Cr2-yO, Fe3-yO4 and Mn1-yO, where y is greater than 0.00001 and less than 0.15. Preferably, y = 0.0001-0.01 for Co1-yO and Cr2-yO; y = 0.001-0.03 for Fe3-yO4; and y = 0.00001-0.1 for Mn1-yO. The metal oxide layer is preferably homogeneous and has thickness of 5-1000 microns , preferably 10-200 microns . The layer containing the metal oxide can comprise a metal or ceramic matrix of thickness 5-1000 microns , preferably 10-100 microns , and containing 5-70 weight %, preferably 10-40 weight %, tribo-active particles of at least one metal oxide having a deficiency of metal cations. Preferably, the tribo-active particles have mean size of 0.3-30 microns , more preferably 0.5-5 microns . Matrix metal is selected from iron, nickel, nickel-phosphorus, chromium, cobalt, tungsten, molybdenum, and alloy of these metals, iron-aluminum, brass (CuZn) or bronze (CuSn). Matrix ceramic is selected from Al2O3, ZrO2, Cr2O3, TiO2 or a mixture of these ceramics. Independent claims are given for: (a) a friction part concerning a cam following, a camshaft, a piston pin, a piston ring, a cylinder liner, a valve guide, a valve rod, a synchronizing cone, or an oil pump gear; and (b) production of the friction part by thermal spraying of powders of the components of the layer on the base of the friction part, or electroplating for composites having a metal matrix of nickel, nickel-phosphorus or chromium.

Description

La présente invention concerne des pièces mécaniques de friction pour moteurs à combustion interne lubrifiés par un fluide, portant un revêtement anti-usure à base d'oxydes métalliques particuliers présentant un défaut stoechiométrique en cations métalliques.The present invention relates to mechanical friction parts for internal combustion engines lubricated by a fluid, bearing a anti-wear coating based on specific metal oxides with a stoichiometric defect in metal cations.

La lubrification des moteurs de véhicules automobiles par des lubrifiants traditionnels à base d'huiles minérales contenant une fraction importante d'additifs (anti-usure, extrême-pression, indice de viscosité, anti-corrosion etc.) pose d'importants problèmes liés d'une part à la toxicité et aux nuisances écologiques que présentent ces huiles moteur, et d'autre part à la nécessité, pour l'utilisateur, de renouveler à des intervalles réguliers ces huiles usées par la dégradation et l'épuisement des additifs.The lubrication of motor vehicle engines by traditional lubricants based on mineral oils containing a fraction important additives (anti-wear, extreme pressure, viscosity index, anti-corrosion etc.) poses important problems linked on the one hand to toxicity and to the ecological nuisances presented by these engine oils, and on the other hand, the need for the user to renew at intervals regular these used oils by the degradation and depletion of additives.

Une approche intéressante pour résoudre ces problèmes a consisté à transférer une partie des fonctions assumées classiquement par l'huile moteur sur des revêtements des pièces mécaniques soumises à des frottements. Les matériaux formant ces revêtements capables de remplir ces fonctions de lubrification seront appelés par la suite matériaux "triboactifs".An interesting approach to solving these problems has consisted in transferring part of the functions conventionally assumed by engine oil on coatings of mechanical parts subjected to friction. The materials forming these coatings capable of filling these lubrication functions will hereinafter be called "triboactive" materials.

La demanderesse a découvert le fait surprenant qu'un groupe de matériaux rarement utilisés en construction mécanique en raison d'importants phénomènes de fluage, présentaient des propriétés lubrifiantes très intéressantes lorsqu'ils étaient utilisés en tant que lubrifiant solide appliqué à la surface des pièces mécaniques de friction du moteur.The Applicant has discovered the surprising fact that a group of materials rarely used in mechanical engineering due to important creep phenomena, had very lubricating properties interesting when used as a solid lubricant applied on the surface of the mechanical friction parts of the engine.

Ces nouveaux matériaux triboactifs sont des oxydes métalliques particuliers présentant un faible défaut en cations métalliques par rapport à la stoechiométrie de l'oxyde-mère.These new triboactive materials are metallic oxides individuals with a weak defect in metal cations compared to to the stoichiometry of the mother oxide.

Ils peuvent être utilisés soit sous forme de revêtement triboactif appliqué à la surface des pièces mécaniques de friction (couche homogène), soit sous forme de particules triboactives dispersées dans une couche métallique ou céramique à la surface des pièces mécaniques de friction (couche composite).They can be used either as a triboactive coating applied to the surface of mechanical friction parts (homogeneous layer), either in the form of triboactive particles dispersed in a layer metallic or ceramic on the surface of mechanical friction parts (composite layer).

L'objet de la présente invention est par conséquent une pièce mécanique de friction pour moteurs à combustion interne revêtue, sur une partie ou sur la totalité de sa surface, d'une couche comprenant au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques.The object of the present invention is therefore a part friction mechanics for coated internal combustion engines, on a part or all of its surface, of a layer comprising at least a metal oxide having a stoichiometric cation defect metallic.

L'invention a également pour objet des procédés de fabrication d'une pièce mécanique de friction pour moteurs à combustion interne revêtue, sur une partie ou sur la totalité de sa surface, d'une couche comprenant au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques.The invention also relates to manufacturing methods of a mechanical friction part for internal combustion engines coated, on part or all of its surface, with a layer comprising at least one metal oxide having a stoichiometric defect of metal cations.

Les oxydes métalliques présentant un défaut stoechiométrique en cations métalliques utilisables selon la présente invention sont choisis notamment parmi les suivants :
   Ni1-yO,
   Co1-yO,
   Cr2-yO.
   Fe1-yO,
   Fe3-yO4
   Mn1-yO où 10-5 < y < 0,15.The metal oxides having a stoichiometric defect in metal cations which can be used according to the present invention are chosen in particular from the following:
Ni 1-y O,
Co 1-y O,
Cr 2-y O.
Fe 1-y O,
Fe 3-y O 4
Mn 1-y O where 10 -5 <y <0.15.

La valeur de y détermine l'importance du fluage et par conséquent les propriétés anti-usure de ces oxydes. The value of y determines the amount of creep and therefore the anti-wear properties of these oxides.

Les oxydes stoechiométriques (y = 0) ont, certes, des propriétés tribologiques mais celles-ci sont très faibles. L'apparition de lacunes d'ions métalliques dans le réseau cristallin de l'oxyde diminue de plusieurs ordres de grandeur la contrainte de fluage et améliore considérablement ses propriétés d'anti-usure.Stoichiometric oxides (y = 0) certainly have properties tribological but these are very weak. The appearance of gaps of metal ions in the crystal lattice of the oxide decreases by several orders of magnitude the creep stress and greatly improves its anti-wear properties.

Les fourchettes préférées pour y varient en fonction des différents oxydes métalliques. Ces fourchettes préférées sont en particulier les suivantes:
   10-4 < y < 10-2 pour Ni1-yO, Co1-yO et Cr2-yO
   10-3 < y < 0,15 pour Fe1-yO,
   10-3 < y < 0,03 pour Fe3-yO4,
   10-5 < y < 0,1 pour Mn1-yOThe preferred ranges for y vary according to the different metal oxides. These preferred ranges are in particular the following:
10 -4 <y <10 -2 for Ni 1-y O, Co 1-y O and Cr 2-y O
10 -3 <y <0.15 for Fe 1-y O,
10 -3 <y <0.03 for Fe 3-y O 4 ,
10 -5 <y <0.1 for Mn 1-y O

L'épaisseur de la couche de matériau triboactif dépend de la nature et de l'architecture du revêtement et du procédé de dépôt choisi et elle sera ajustée en fonction des contraintes tribologiques auxquelles sera soumise la pièce.The thickness of the layer of triboactive material depends on the nature and architecture of the coating and the deposition process chosen and it will be adjusted according to the tribological constraints to which submitted the piece.

Plus particulièrement, lorsque l'oxyde métallique présentant un défaut stoechiométrique en cations métalliques est appliqué sous forme d'un revêtement homogène, l'épaisseur de ce revêtement est généralement comprise entre 5 µm et 1000 µm, et de préférence entre 10 µm et 200 µm, à l'état opérationnel.More particularly, when the metal oxide having a stoichiometric defect in metal cations is applied in the form of a homogeneous coating, the thickness of this coating is generally between 5 µm and 1000 µm, and preferably between 10 µm and 200 µm, at operational status.

Lorsque l'oxyde métallique est présent sous forme de particules dans une matrice métallique ou céramique (revêtement composite), l'épaisseur de cette matrice contenant des particules triboactives est comprise entre 5 µm et 1000 µm, et de préférence entre 10 µm et 100 µm, à l'état opérationnel.When the metal oxide is present in the form of particles in a metallic or ceramic matrix (composite coating), the thickness of this matrix containing triboactive particles is included between 5 µm and 1000 µm, and preferably between 10 µm and 100 µm, at operational status.

Comme indiqué ci-dessus, la matrice de la couche composite tri-boactive de la présente invention peut être une matrice métallique ou céramique.As indicated above, the matrix of the tri-boactive composite layer of the present invention may be a metallic or ceramic matrix.

On peut citer à titre d'exemples de matrices métalliques des matrices en fer, en nickel, en nickel-phosphore, en chrome, en cobalt, en tungstène, en molybdène, en un alliage de ces métaux, ou en fonte de fer et d'aluminium, en laiton (CuZn) ou en bronze (CuSn).As examples of metallic matrices, mention may be made of iron, nickel, nickel-phosphorus, chromium, cobalt, tungsten, molybdenum, an alloy of these metals, or cast iron and aluminum, brass (CuZn) or bronze (CuSn).

Des matrices céramiques utilisables pour les revêtements composites selon la présente invention sont par exemple à base d'Al2O3, de ZrO2, de Cr2O3, de TiO2 ou d'un mélange de ceux-ci.Ceramic matrices which can be used for the composite coatings according to the present invention are for example based on Al 2 O 3 , ZrO 2 , Cr 2 O 3 , TiO 2 or a mixture of these.

La taille moyenne des particules triboactives en oxydes métalliques présentant un défaut stoechiométrique en cations métalliques utilisées selon la présente invention est généralement comprise entre 0,3 et 30 µm, de préférence entre 0,5 et 5 µm.The average size of triboactive metal oxide particles presenting a stoichiometric defect in metallic cations used according to the present invention is generally between 0.3 and 30 µm, preferably between 0.5 and 5 µm.

Elles sont présentes dans la matrice métallique ou céramique à raison de 5 % à 70 % en poids, de préférence à raison de 10 % à 40 % en poids rapporté au poids total de la couche composite (matrice + particules). Pour une teneur inférieure à 5 %, l'efficacité anti-usure du revêtement est insuffisante. Au-delà de 70 % en poids, il y a, pour la plupart des matrices céramiques et métalliques, un risque de manque de cohésion et/ou d'adhésion de la couche composite.They are present in the metallic or ceramic matrix to from 5% to 70% by weight, preferably from 10% to 40% by weight relative to the total weight of the composite layer (matrix + particles). For a content of less than 5%, the anti-wear effectiveness of the coating is insufficient. Above 70% by weight, there are, for the most part ceramic and metallic matrices, a risk of lack of cohesion and / or adhesion of the composite layer.

Les revêtements triboactifs de la présente invention conviennent uniquement pour des pièces mécaniques de friction soumises, dans le moteur, à des contraintes de glissement. On peut citer en particulier les poussoirs, cames d'arbres à cames, axes de piston, segments, chemises, guides de soupape, tiges de soupape, anneaux de synchronisation et engrenages de pompe à huile.The triboactive coatings of the present invention are suitable only for mechanical friction parts submitted, in the motor, to sliding constraints. We can mention in particular the lifters, camshaft cams, piston pins, segments, liners, valve guides, valve stems, timing rings and gears oil pump.

Les revêtements anti-usure à base d'oxydes métalliques présentant un défaut stoechiométrique en cations peuvent être déposés à la surface des pièces mécaniques par projection thermique ou par dépôt galvanique.Anti-wear coatings based on metal oxides with a stoichiometric defect in cations can be deposited on the surface mechanical parts by thermal spraying or by galvanic deposition.

Pour la projection thermique, on applique soit une fine poudre de l'oxyde métallique présentant un défaut stoechiométrique de cations métalliques, soit un mélange d'une telle poudre avec une poudre formant la matrice du revêtement composite, à savoir une poudre métallique ou une poudre céramique.For thermal spraying, either a fine powder of metal oxide having a stoichiometric cation defect metallic, or a mixture of such a powder with a powder forming the matrix of the composite coating, namely a metallic powder or a ceramic powder.

Le dépôt galvanique convient surtout pour les revêtements composites à matrice métallique en nickel, en nickel-phosphore ou en chrome.Galvanic deposition is especially suitable for composite coatings with metallic matrix in nickel, nickel-phosphorus or chromium.

Claims (13)

Pièce mécanique de friction pour moteurs à combustion interne revêtue, sur une partie ou sur la totalité de sa surface, d'une couche comprenant au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques, choisi parmi Co1-yO, Cr2-yO, Fe3-yO4 et Mn1-yO avec 10-5 < y < 0,15.Mechanical friction part for internal combustion engines coated, on part or all of its surface, with a layer comprising at least one metal oxide having a stoichiometric defect in metal cations, chosen from Co 1 -y O, Cr 2 -y O, Fe 3-y O 4 and Mn 1-y O with 10 -5 <y <0.15. Pièce mécanique de friction selon la revendication 1, caractérisée par le fait que
   10-4 < y < 10-2 pour CO1-yO et Cr2-yO,
   10-3 < y < 0,03 pour Fe3-yO4, et
   10-5 < y < 0,1 pour Mn1-yO.Mechanical friction part according to claim 1, characterized in that
10 -4 <y <10 -2 for CO 1-y O and Cr 2-y O,
10 -3 <y <0.03 for Fe 3-y O 4 , and
10 -5 <y <0.1 for Mn 1-y O. Pièce mécanique de friction selon la revendication 1 ou 2, caractérisée par le fait que ladite couche comprenant au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques est une couche homogène.Mechanical friction part according to claim 1 or 2, characterized in that said layer comprising at least one metal oxide with stoichiometric cation defect metallic is a homogeneous layer. Pièce mécanique de friction selon la revendication 3, caractérisée par le fait que l'épaisseur de la couche homogène d'oxyde(s) métallique(s) présentant un défaut stoechiométrique de cations métalliques est comprise entre 5 µm et et 1000 µm, de préférence entre 10 µm et 200 µm.Mechanical friction part according to claim 3, characterized by the fact that the thickness of the homogeneous layer of metal oxide (s) having a stoichiometric defect of metal cations is between 5 µm and 1000 µm, preferably between 10 µm and 200 µm. Pièce mécanique de friction selon l'une des revendications 1 à 4, caractérisée par le fait que ladite couche comprenant au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques est constituée d'une matrice métallique ou céramique contenant des particules triboactives d'au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques.Mechanical friction part according to one of claims 1 to 4, characterized in that said layer comprising at least a metal oxide having a stoichiometric cation defect metallic consists of a metallic or ceramic matrix containing triboactive particles of at least one metal oxide having a stoichiometric defect in metal cations. Pièce mécanique de friction selon la revendication 5, caractérisée par le fait que ladite matrice métallique contenant les particules triboactives est constituée de fer, de nickel, de nickel-phosphore, de chrome, de cobalt, de tungstène, de molybdène, d'un alliage de ces métaux, ou de fonte de fer et d'aluminium, de laiton (CuZn) ou de bronze (CuSn).Mechanical friction part according to claim 5, characterized by the fact that said metallic matrix containing the particles triboactive consists of iron, nickel, nickel-phosphorus, chromium, cobalt, tungsten, molybdenum, an alloy of these metals, or of cast iron and aluminum, brass (CuZn) or bronze (CuSn). Pièce mécanique de friction selon la revendication 5, caractérisée par le fait que ladite matrice céramique contenant les particules triboactives est constituée de Al2O3, ZrO2, de Cr2O3, de TiO2 ou d'un mélange de ceux-ci.Mechanical friction part according to claim 5, characterized in that the said ceramic matrix containing the triboactive particles consists of Al 2 O 3 , ZrO 2 , Cr 2 O 3 , TiO 2 or a mixture thereof . Pièce mécanique de friction selon l'une quelconque des revendications 5 à 7, caractérisée par le fait que l'épaisseur de ladite matrice céramique ou métallique renfermant des particules triboactives est comprise entre 5 µm et 1000 µm, et de préférence entre 10 µm et 100 µm.Mechanical friction part according to any one of claims 5 to 7, characterized in that the thickness of said ceramic or metallic matrix containing triboactive particles is between 5 µm and 1000 µm, and preferably between 10 µm and 100 µm. Pièce mécanique de friction selon l'une quelconque des revendications 5 à 8, caractérisée par le fait que lesdites particules triboactives ont une taille moyenne comprise entre 0,3 et 30 µm, de préférence entre 0,5 et 5 µm.Mechanical friction part according to any one of Claims 5 to 8, characterized in that the said triboactive particles have an average size of between 0.3 and 30 µm, preferably between 0.5 and 5 µm. Pièce mécanique de friction selon l'une quelconque des revendications 5 à 9, caractérisée par le fait que ladite matrice céramique ou métallique contient de 5 % à 70 % en poids, de préférence de 10 % à 40 % en poids de particules triboactives.Mechanical friction part according to any one of Claims 5 to 9, characterized in that the said ceramic matrix or metallic contains from 5% to 70% by weight, preferably 10% to 40% by weight of triboactive particles. Pièce mécanique de friction selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'il s'agít d'un poussoir, d'une came d'arbre à cames, d'un axe de piston, d'un segment, d'une chemise, d'un guide de soupape, d'une tige de soupape, d'un anneau de synchronisation ou d'un engrenage de pompe à huile.Mechanical friction part according to any one of previous claims, characterized in that it is a pusher, camshaft cam, piston pin, segment, a jacket, a valve guide, a valve stem, a synchronization ring or an oil pump gear. Procédé de fabrication d'une pièce mécanique de friction selon l'une quelconque des revendications précédentes, caractérisé par le fait que l'on applique par projection thermique - sur une partie ou sur la totalité de la surface d'une pièce de base - une poudre d'au moins un oxyde métallique présentant un défaut stoechiométrique de cations métalliques, ou un mélange d'une poudre d'au moins un oxyde métallique présentant un défaut stoechiométrique en cation et d'une poudre métallique ou céramique.Method of manufacturing a mechanical friction part according to any one of the preceding claims, characterized by the fact that we apply by thermal spraying - on a part or over the entire surface of a basic part - a powder of at least minus a metal oxide having a stoichiometric defect of metal cations, or a mixture of a powder of at least one oxide metallic with a stoichiometric cation defect and a metallic or ceramic powder. Procédé de fabrication d'une pièce mécanique de friction selon l'une quelconque des revendications 5,6 et 8 à 11, caractérisé par le fait que l'on applique par dépôt galvanique - sur une partie ou sur la totalité de la surface d'une pièce de hase - un mélange d'une poudre d'au moins un oxyde métallique présentant un défaut stoechiométrique en cation et d'un métal choisi parmi le nickel, le nickel-phosphore et le chrome.Method of manufacturing a mechanical friction part according to any one of claims 5,6 and 8 to 11, characterized by the fact that we apply by galvanic deposition - on a part or on the entire surface of a hase piece - a mixture of a powder at least one metal oxide having a stoichiometric defect in cation and of a metal chosen from nickel, nickel-phosphorus and chrome.
EP00401715A 1999-06-16 2000-06-16 Sliding part coated with triboactive oxides having a deficiency of metal cations Withdrawn EP1061153A1 (en)

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FR9907630A FR2795095B1 (en) 1999-06-16 1999-06-16 MECHANICAL FRICTION PART COVERED WITH TRIBOACTIVE OXIDES HAVING A DEFECT OF METAL CATIONS
FR9907630 1999-06-16

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
GB2367074A (en) * 2000-07-21 2002-03-27 Ford Global Tech Inc Multi-layer valve guides
US6726216B2 (en) * 2001-06-01 2004-04-27 Federal-Mogul Friedberg Gmbh Piston ring with oxide-nitride composite layer
US7445763B2 (en) 2001-03-05 2008-11-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Coating powder of Cr or V doped titanium suboxides
US8020529B2 (en) * 2006-02-27 2011-09-20 Daimler Ag Piston pin with slide layer for connecting rod eye for internal combustion engines
DE102015209887A1 (en) * 2015-05-29 2016-12-01 Mahle International Gmbh Piston for a cylinder of an internal combustion engine

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DE19651094A1 (en) * 1996-12-09 1998-06-10 Man Technologie Gmbh Dry frictional contact system for high temperature use

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WO1997013884A1 (en) * 1995-10-06 1997-04-17 Ford Motor Company Limited Method of depositing composite metal coatings
DE19548718C1 (en) * 1995-12-23 1997-05-28 Daimler Benz Ag Cylinder liner for motor vehicle IC-engine
DE19651094A1 (en) * 1996-12-09 1998-06-10 Man Technologie Gmbh Dry frictional contact system for high temperature use

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2367074A (en) * 2000-07-21 2002-03-27 Ford Global Tech Inc Multi-layer valve guides
GB2367074B (en) * 2000-07-21 2004-05-12 Ford Global Tech Inc Multi-layer valve guides
US7445763B2 (en) 2001-03-05 2008-11-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Coating powder of Cr or V doped titanium suboxides
US6726216B2 (en) * 2001-06-01 2004-04-27 Federal-Mogul Friedberg Gmbh Piston ring with oxide-nitride composite layer
US8020529B2 (en) * 2006-02-27 2011-09-20 Daimler Ag Piston pin with slide layer for connecting rod eye for internal combustion engines
DE102015209887A1 (en) * 2015-05-29 2016-12-01 Mahle International Gmbh Piston for a cylinder of an internal combustion engine

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FR2795095B1 (en) 2002-04-12

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