EP1022351B1 - Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur - Google Patents

Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur Download PDF

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Publication number
EP1022351B1
EP1022351B1 EP99811122A EP99811122A EP1022351B1 EP 1022351 B1 EP1022351 B1 EP 1022351B1 EP 99811122 A EP99811122 A EP 99811122A EP 99811122 A EP99811122 A EP 99811122A EP 1022351 B1 EP1022351 B1 EP 1022351B1
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EP
European Patent Office
Prior art keywords
accordance
weight percent
powder
layer
particle size
Prior art date
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Expired - Lifetime
Application number
EP99811122A
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German (de)
English (en)
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EP1022351B2 (fr
EP1022351A1 (fr
Inventor
Gérard BARBEZAT
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.)
Oerlikon Metco AG
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Sulzer Metco AG
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Application filed by Sulzer Metco AG filed Critical Sulzer Metco AG
Priority to EP04011394A priority Critical patent/EP1507020B1/fr
Publication of EP1022351A1 publication Critical patent/EP1022351A1/fr
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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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
    • B05B7/1404—Arrangements for supplying particulate material
    • B05B7/1431—Arrangements for supplying particulate material comprising means for supplying an additional liquid
    • B05B7/1436—Arrangements for supplying particulate material comprising means for supplying an additional liquid to a container where the particulate material and the additional liquid are brought together
    • 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
    • C23C4/08—Metallic material containing only metal elements
    • 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

Definitions

  • the invention relates to an applied by plasma spraying iron-containing layer for cylinder surfaces engine blocks according to claim 1 and a method of manufacture Such layers according to claim 6 or 7.
  • the coating of bores by means of the plasma spraying process has long been known. Different metallic materials can be applied.
  • the layers are passed through Diamanthonen edited to the final dimensions and provided with the desired topography.
  • the workability of the layers and the tribological properties are by the microstructure and the physical properties of the corresponding layers decisively influenced.
  • the object of the present invention is the machinability and the tribological properties of plasma-sprayed iron-containing layers for cylinder liners of engine blocks.
  • the invention is based on the surprising finding that in a particularly controlled Reaction of the powder used with oxygen during plasma spraying a microstructure can be produced which excellent in machinability and tribology Features. In particular, the friction coefficients and the Tendency to scuffing ("eating", ie the onset of adhesive wear) drastically reduced.
  • Preferred embodiments of the applied by plasma spraying layers are in the dependent claims 2 to 5 circumscribed.
  • the content of Fe 2 O 3 is less than 0.2% by weight.
  • the amount of oxides formed can be further influenced by mixing the air with nitrogen or oxygen. Replacing the air with pure oxygen reduces the bound level of oxygen in the layer by a factor of about two.
  • a gas amount of 40 to 200 NLPM of oxygen is added.
  • the velocity of the gas flow in the cylinder bore or sleeve during coating is 7 to 12 m / s.
  • Fe Difference to 100% by weight
  • the volume of FeO and Fe 3 O 4 can be influenced by selecting the particle size distribution.
  • the particle size of the powder is in the range of 5 to 25 microns, 10 to 45 microns or 15 to 60 microns. It can be determined by means of an optical or electronic microscope, in particular a scanning electron microscope SEM, or by the MICROTRAC laser diffraction method.
  • the oxide ceramic consists of TiO 2 or Al 2 O 3 TiO 2 and / or Al 2 O 3 ZrO 2 alloy systems.
  • the proportion of oxide ceramics in the powder used is preferably 5 to 50% by weight.
  • the choice of the optimum size of the powder particles is taking into account the tribological Properties of the layers produced and the mechanical behavior of the System layer substrate met.
  • the powder may also contain small amounts (0.01-0.2 wt%) of S and P.
  • the particle size of the powder was between 5 to 25 microns, and the production took place by gas atomizing.
  • the velocity of the gas flow during coating of the can was 10 m / s, the amount of air for the layer cooling and powder reaction 500 NLPM (corresponding 100 NLPM oxygen). This amount of air was supplied through a PlasmatronMech, e.g. a plasmatron according to EP-B1-0 645 946.
  • the results of the investigations carried out show that the oxygen content in the produced layer is 3% by weight.
  • the oxygen is bound according to investigations by means of X-ray fine structure analysis under the stoichiometric formulas FeO and Fe 3 O 4 . These studies also determined that the formation of Fe 2 O 3 is below the detection limit.
  • Example 1 When using a powder of the same chemical composition as in Example 1, but with a particle size of 10 to 45 microns, and otherwise under the same boundary conditions as in Example 1, the proportion of bound oxygen in the generated Layers at 2% by weight. The remaining results of an analysis of the so applied Layer were the same as in Example 1.
  • the particle size of the powder was between 10 to 45 microns, and the production took place by gas atomizing.
  • Example 2 To the powder according to Example 2, an amount of 30% by weight of an alloyed ceramic powder consisting of 60% by weight of Al 2 O 3 and 40% by weight of TiO 2 was added.
  • the layers produced by means of this powder mixture are mechanically reinforced by the incorporation of the ceramic particles (particle size 5 to 22 ⁇ m).
  • Example 4 Analogously to Example 4, 30% by weight of an alloyed ceramic powder consisting of 80% by weight of Al 2 O 3 and 20% by weight of ZrO 2 was added. The layers produced by means of this powder mixture are mechanically reinforced by the incorporation of the ceramic particles (particle size 5 to 22 ⁇ m). The same effect as in Example 4 was achieved.
  • Fig. 1 shows a diagram from which the reduction of the friction coefficient in dependence on the particle size of the powder and the mechanical behavior, namely the adhesive strength of the layer on AlSi substrates, depending on the particle size of the powder.
  • the coefficient of friction with increasing size of the particles of the coating powder reduced.
  • the adhesive strength of the layer on AISi substrates decreases as the size of the particles of the coating powder increases.
  • the particle size to be chosen can be in the range of 25-30 m, so that with a sufficient adhesive strength in most cases the Layer in the range of 45-50 MPa is to be expected, the coefficient of friction, in comparison with layers according to the prior art, by about 22-25% less.
  • Fig. 2 shows a diagram from which the reduction of the friction coefficient in dependence from the amount of bound oxygen in the layer and the mechanical Behavior, namely the adhesion of the layer on AlSi substrates, depending on from the amount of bound oxygen in the layer. From the On the one hand, the diagram clearly shows that the coefficient of friction increases with increasing Amount of bound oxygen in the layer reduced. On the other hand, it becomes clear that the adhesion of the layer to AlSi substrates decreases when the amount of bound oxygen in the layer increases.
  • a good compromise regarding the aspired one Amount of bound oxygen in the layer may be in the range of 2-2.5 Wt .-% are, so that with a sufficient in most cases, the adhesive strength Layer in the range of 40-50 MPa is to be expected, the coefficient of friction, in comparison with layers according to the prior art, is about 20-25% less. If but, as already explained in connection with Fig. 1, a pronounced in the first place high adhesion of the layer is sought and the reduction of the coefficient of friction is rather of minor importance, you will have a coating with a Aim at less than 2% by weight bound oxygen. On the other hand, if primarily a very low coefficient of friction is sought and a slightly lower bond strength can be accepted, one becomes one Select a layer with a bound oxygen content of more than 2.5 wt .-%.

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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)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (20)

  1. Couche contenant du fer appliquée par jet de plasma pour des alésages de cylindres de blocs-moteurs, caractérisée en ce que la teneur en oxygène lié est de 1 à 4% en poids et l'oxygène lié forme avec le fer des cristaux de FeO et Fe3O4.
  2. Couche selon la revendication 1, caractérisée en ce que la teneur en Fe2O3 est de moins de 0,2% en poids.
  3. Couche selon la revendication 1 ou 2, caractérisée en ce que le substrat pour la couche à appliquer est le bloc-moteur lui-même se composant d'un alliage d'aluminium ou de magnésium ou de fonte.
  4. Couche selon la revendication 1 ou 2, caractérisée en ce que le substrat pour la couche à appliquer est une fourrure en fonte introduite dans un bloc-moteur en un alliage d'aluminium ou de magnésium.
  5. Couche selon la revendication 3 ou 4, caractérisée en ce que la fonte est mélangée à du graphite lamellaire ou vermiculaire.
  6. Procédé pour la production de couches selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le matériau d'enduction est introduit en forme de poudre et on ajoute, pendant le jet de plasma, une quantité d'air de 200 à 1000 LNPM.
  7. Procédé pour la production de couches selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le matériau d'enduction est fourni sous forme de poudre et est additionné, pendant le jet de plasma, d'une quantité de gaz avec 40 à 200 LNPM d'oxygène.
  8. Procédé selon la revendication 7, caractérisé en ce que pendant le jet de plasma, on ajoute de l'oxygène pur.
  9. Procédé selon l'une quelconque des revendications 6 à 8, caractérisé en ce que la vitesse du flux de gaz à l'intérieur de l'alésage du cylindre à enduire ou respectivement de la fourrure pendant l'enduction est de 7 à 12 m/s.
  10. Procédé selon l'une quelconque des revendications 6 à 9, caractérisé en ce que pour l'enduction, on utilise une poudre atomisée au gaz de la composition chimique qui suit : C = 0,4 à 1,5% en poids Cr = 0,2 à 2,5% en poids Mn = 0,2 à 3% en poids Fe = différence à 100% en poids
  11. Procédé selon l'une quelconque des revendications 6 à 9, caractérisé en ce que pour l'enduction, on utilise une poudre atomisée au gaz de la composition chimique qui suit : C = 0,1 à 0,8% en poids Cr = 11 à 18% en poids Mn = 0,1 à 1,5% en poids Mo = 0,1 à 5% en poids Fe = différence à 100% en poids
  12. Procédé selon la revendication 10 ou 11, caractérisé en ce que la poudre contient de plus : S = 0,01 à 0,2% en poids P = 0,01 à 0,1% en poids
  13. Procédé selon l'une quelconque des revendications 6 à 12, caractérisé en ce que le volume de FeO et Fe3O4 est influencé par le choix de la granulométrie.
  14. Procédé selon la revendication 13, caractérisé en ce que la grandeur des particules de la poudre se trouve dans la zone de 5 à 25 µm.
  15. Procédé selon la revendication 13, caractérisé en ce que la grandeur des particules de la poudre est dans la zone de 10 à 45 µm.
  16. Procédé selon la revendication 13, caractérisé en ce que la grandeur des particules de la poudre est dans la zone de 15 à 60 µm.
  17. Procédé selon l'une quelconque des revendications 10 à 16, caractérisé en ce qu'on utilise une poudre obtenue par atomisation au gaz au moyen d'argon ou d'azote.
  18. Procédé selon l'une quelconque des revendications 10 à 17, caractérisé en ce qu'on utilise une poudre modifiée par addition d'une céramique d'oxyde tribologique.
  19. Procédé selon la revendication 18, caractérisé en ce qu'une céramique d'oxyde, qui se compose de TiO2 ou de systèmes d'alliages de Al2O3TiO2 et/ou Al2O3ZrO2 est utilisée.
  20. Procédé selon la revendication 18 ou 19, caractérisé en ce que la part de céramique d'oxyde dans la poudre utilisée est de 5 à 50% en poids.
EP99811122A 1999-01-19 1999-12-08 Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur Expired - Lifetime EP1022351B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04011394A EP1507020B1 (fr) 1999-01-19 1999-12-08 Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH9199 1999-01-19
CH9199 1999-01-19
CH24599 1999-02-09
CH24599 1999-02-09

Related Child Applications (1)

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EP04011394A Division EP1507020B1 (fr) 1999-01-19 1999-12-08 Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur

Publications (3)

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EP1022351A1 EP1022351A1 (fr) 2000-07-26
EP1022351B1 true EP1022351B1 (fr) 2004-05-19
EP1022351B2 EP1022351B2 (fr) 2009-02-25

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EP99811122A Expired - Lifetime EP1022351B2 (fr) 1999-01-19 1999-12-08 Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur
EP04011394A Expired - Lifetime EP1507020B1 (fr) 1999-01-19 1999-12-08 Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur

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EP04011394A Expired - Lifetime EP1507020B1 (fr) 1999-01-19 1999-12-08 Couche déposée par jet de plasma sur des alésages de cylindres de blocs moteur

Country Status (9)

Country Link
US (2) US6548195B1 (fr)
EP (2) EP1022351B2 (fr)
JP (2) JP3967511B2 (fr)
KR (1) KR100593342B1 (fr)
AT (2) ATE267275T1 (fr)
CA (1) CA2296155C (fr)
DE (2) DE59909522D1 (fr)
ES (2) ES2221343T5 (fr)
PT (2) PT1022351E (fr)

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EP2664684A2 (fr) 2012-05-14 2013-11-20 Stahlwerk Ergste Westig GmbH Acier chromé à haute dureté et résistance à la corrosion ainsi que son utilisation pour protéger les surfaces métalliques
WO2017137500A1 (fr) 2016-02-12 2017-08-17 Oerlikon Surface Solutions Ag, Päffikon Système tribologique d'un moteur à combustion interne pourvu d'un revêtement

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JP7083295B2 (ja) * 2018-08-22 2022-06-10 トヨタ自動車東日本株式会社 摺動部材及びその製造方法
JP7159111B2 (ja) * 2019-05-28 2022-10-24 日本ピストンリング株式会社 摺動部材と潤滑油との組み合わせ

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CA2296155E (fr) 2000-07-19
DE59909522D1 (de) 2004-06-24
ES2221343T5 (es) 2009-06-12
JP3967511B2 (ja) 2007-08-29
US6548195B1 (en) 2003-04-15
ES2221343T3 (es) 2004-12-16
JP2007191795A (ja) 2007-08-02
KR100593342B1 (ko) 2006-06-26
ATE365814T1 (de) 2007-07-15
US6572931B2 (en) 2003-06-03
JP2000212717A (ja) 2000-08-02
KR20000071238A (ko) 2000-11-25
EP1507020B1 (fr) 2007-06-27
CA2296155C (fr) 2004-09-14
EP1022351B2 (fr) 2009-02-25
US20020051851A1 (en) 2002-05-02
PT1507020E (pt) 2007-07-13
ATE267275T1 (de) 2004-06-15
JP4644687B2 (ja) 2011-03-02
PT1022351E (pt) 2004-10-29
ES2288232T3 (es) 2008-01-01
EP1507020A2 (fr) 2005-02-16
DE59914394D1 (de) 2007-08-09
EP1507020A3 (fr) 2005-04-20
CA2296155A1 (fr) 2000-07-19
EP1022351A1 (fr) 2000-07-26

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