EP1896626B1 - Procede pour munir une chemise de cylindre d'un revetement - Google Patents

Procede pour munir une chemise de cylindre d'un revetement Download PDF

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Publication number
EP1896626B1
EP1896626B1 EP06761655A EP06761655A EP1896626B1 EP 1896626 B1 EP1896626 B1 EP 1896626B1 EP 06761655 A EP06761655 A EP 06761655A EP 06761655 A EP06761655 A EP 06761655A EP 1896626 B1 EP1896626 B1 EP 1896626B1
Authority
EP
European Patent Office
Prior art keywords
coating
alloy
layer
sprayed
cylinder
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.)
Not-in-force
Application number
EP06761655A
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German (de)
English (en)
Other versions
EP1896626A1 (fr
Inventor
Gerhard Bucher
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.)
Mahle International GmbH
Original Assignee
Mahle International GmbH
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 Mahle International GmbH filed Critical Mahle International GmbH
Publication of EP1896626A1 publication Critical patent/EP1896626A1/fr
Application granted granted Critical
Publication of EP1896626B1 publication Critical patent/EP1896626B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame 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
    • C23C4/131—Wire arc spraying

Definitions

  • the invention relates to a method for coating a cylinder liner according to the preamble of claim 1.
  • Cylinder crankcases are usually made of light metal, especially aluminum, cast, due to the poor tribological properties of light metals, the necessity exists to pour cylinder liners made of an iron-based material, such as gray cast iron, in the cylinder crankcase with. This results in the problems of anchoring the cylinder liners sufficiently firmly in the cylinder crankcase, and to ensure sufficient heat transfer between the cylinder liners and the cylinder crankcase. These problems can be solved by giving the outer surfaces of the cylinder liners a roughcast structure with undercuts. However, this entails that the webs between the cast-in cylinder liners in the cylinder liners are very wide, and therefore that the space requirement of the cylinder liners is very large.
  • Such a cylinder liner made of gray cast iron is in the patent DE 197 29 017 C2 described. This has on its outer surface applied by flame spraying or by arc spraying surface layer of an AlSi alloy containing less than 15% silicon. On this cover layer, an oxidation protection layer is applied, which consists of a zinc alloy, and whose task is to prevent the oxidation of the AlSi layer, whereby the metallic bonding of the cover layer is prevented with the Umgussmaterial the cylinder crankcase.
  • the disadvantage here is that the AlSi alloy is already oxidized during the spraying of the cover layer.
  • the resulting oxide skin adheres very firmly to the AlSi layer.
  • their melting temperature is higher than the achievable temperatures during encapsulation.
  • the oxide skin is indeed removable, but it forms after removal very quickly again, so that an additionally applied protective layer of zinc or a zinc alloy does not ensure a metallic bond between the AlSi layer and the Umgussmaterial the cylinder crankcase can.
  • the thermal expansion coefficient of the AlSi cover layer is about 1.7 times the thermal expansion coefficient of gray cast iron, so that arise in temperature changes stresses in the known layer system that affect the bond between the cylinder liner and the cylinder crankcase.
  • the gradation of the thermal expansion coefficients in the layer structure according to the invention between the cast iron bushing, the layer system and the Umgussmaterial the cylinder crankcase significantly reduces the thermal stresses in the layer structure according to the invention.
  • the gradation of the melting temperatures, starting from the cylinder liner, through the layer system of the invention to the Umgussmaterial the cylinder crankcase causes a dissolution or a diffusion-based alloying of the outer layer with the Umgussmaterial, which causes a stable metallic bond between the cylinder liner and the Umgussmaterial the cylinder crankcase.
  • the coating consisting of the alloys according to the invention has the advantage that its alloying constituents participate in the precipitation hardening in the bonding zone.
  • a cylinder liner which consists of an iron-based material that may be alloyed or unalloyed.
  • the cylinder liner is made of gray cast iron, which may contain either lamellar graphite, vermicular graphite or nodular graphite.
  • the gray cast iron can in this case have a ferritic-pearlitic, a pearlitic, a bainitic or an austenitic basic structure.
  • the outer surface of the cylinder liner may be smooth. But it can also have all other surface finishes to a flat Raugussober Structure.
  • the cylinder liner may have a machined outer surface.
  • the cylinder crankcase is made of one of the common light metal casting material, both aluminum-based and magnesium-based casting materials in question.
  • the outer surface of the cylinder liner is coated by thermal spraying. In preparation for this, it is necessary to clean the outer surface of dirt and oxides and then roughen. Suitable methods for this are brushing and / or blasting. In particular, blasting with coarse corundum, ie with crystallized Al 2 O 3 , is suitable for this purpose.
  • a first layer is applied to the outer surface of the cylinder liner by thermal spraying.
  • This first layer consists either of 99.9% copper, a CuAl8 alloy, a CuAl8Ni2 alloy, a CuP8 alloy, a CuSi3 alloy or a CuZn37 alloy (brass).
  • the aim here is a low-pore and low-oxide layer with a thickness between 60 ⁇ m and 130 ⁇ m.
  • a further layer of one of the aforementioned copper alloys whose melting temperature is lower than that of copper but whose melting temperature is higher than that of the material constituting the outer coating hereinafter referred to as the second layer.
  • wires of the alloys mentioned in the trade is available, is preferably applied as a thermal spraying method, the wire flame spraying, wherein the melted wire-shaped spray additive in the center of an acetylene-oxygen flame and is sprayed by means of a nebulizer gas, such as compressed air or nitrogen, on the outer surface of the cylinder liner.
  • a nebulizer gas such as compressed air or nitrogen
  • arc wire spraying wherein two wire-shaped spray additives are melted in an arc and thrown by means of a Zerstäubergases on the outer surface of the cylinder liner.
  • two wire-shaped spray additives are melted in an arc and thrown by means of a Zerstäubergases on the outer surface of the cylinder liner.
  • the composition of the layer produced thereby can be varied within wide ranges.
  • copper and zinc wire it is possible to apply a CuZn alloy with up to 45% zinc to the outer surface of the cylinder liner.
  • nitrogen or argon as a sputtering gas oxidation of the materials is largely prevented.
  • One way to further reduce the oxidation of the sprayed material and the oxide content of the sprayed layer is to apply the cold gas spraying method, with unmelted and heated only to a few hundred degrees powder particles to a speed between 300m / sec. and 1200 m / sec. accelerated and sprayed onto the outer surface of the cylinder liner. Due to micro-friction due to the impact of the powder particles, the temperature at the contact surface increases and leads to micro-welding of the powder particles with the outer surface of the cylinder liner.
  • Applicable is also the high-speed flame spraying (HVOF spraying), wherein a continuous gas combustion takes place with high pressures within a combustion chamber, in the central axis of the powdery spray additive is supplied.
  • HVOF spraying high-speed flame spraying
  • the high pressure generated in the combustion chamber of the fuel gas-oxygen mixture produces a high particle velocity, which leads to very dense spray coatings with good adhesion properties.
  • the functions of the first layer are to ensure good adhesion of the first layer to the gray cast iron of the cylinder liner, to provide good bond requirements for a second layer, and a gradation of melt temperatures, ie, a gradual transition of melt temperatures of the gray cast iron of the cylinder liner over the To realize first layer and the second layer up to the Umgussmetall the cylinder crankcase. In addition, this causes a gradation of the thermal expansion coefficients, starting from the cylinder liner over the first and the second layer up to the light metal of the cylinder crankcase.
  • the second layer is applied to the first layer using one of the above-mentioned thermal spraying methods.
  • a Zn85Al15 alloy with 85% zinc and 15% aluminum is preferably used.
  • the aluminum content may vary between 3% and 20%.
  • the aim is a pore and low-oxide layer with a thickness between 60 .mu.m and 130 .mu.m.
  • the function of the second layer is to adhere well to the first layer.
  • the 15 wt.% Aluminum AlZn alloy has a melting point of 450 ° C, which causes the second layer to melt from its encapsulation material during casting of the cylinder crankcase, thereby ensuring metallic bonding between the cylinder liner and the cylinder crankcase encapsulant becomes.
  • the AlZn alloy forms a very thin oxide layer, this does not hinder the bond between cylinder liner and crankcase. Nevertheless, it is advantageous to add a few wt.% Of copper to the AlZn alloy, since this completely prevents the formation of the oxide layer, which brings about a further improvement in the bond between cylinder liner and crankcase.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Claims (13)

  1. Procédé permettant de munir d'un revêtement une chemise de cylindre constituée d'un matériau à base de fer, sachant qu'une première couche et une seconde couche en alliage de zinc sont pulvérisées sur la surface extérieure de la chemise de cylindre au moyen d'un procédé de pulvérisation thermique,
    caractérisé par les étapes suivantes :
    - Pulvérisation de cuivre ou d'un alliage à base de cuivre.
    - Pulvérisation sur la première couche d'un alliage zinc-aluminium composé de Zn avec une teneur pondérale d'aluminium comprise entre 3 et 20 %, en tant que seconde couche.
  2. Procédé selon la revendication 1, caractérisé en ce que du cuivre à 99,9 % est pulvérisé en tant que première couche.
  3. Procédé selon la revendication 1, caractérisé en ce qu'un alliage CuAl8 est pulvérisé en tant que première couche.
  4. Procédé selon la revendication 1, caractérisé en ce qu'un alliage CuAl8Ni2 est pulvérisé en tant que première couche.
  5. Procédé selon la revendication 1, caractérisé en ce qu'un alliage CuP8 est pulvérisé en tant que première couche.
  6. Procédé selon la revendication 1, caractérisé en ce qu'un alliage CuSi3 est pulvérisé en tant que première couche.
  7. Procédé selon la revendication 1, caractérisé en ce qu'un alliage CuZn avec une teneur pondérale de zinc allant jusqu'à 45 % est pulvérisé en tant que première couche.
  8. Procédé selon la revendication 7, caractérisé en ce qu'un alliage CuZn37 est pulvérisé en tant que première couche.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que la première couche présente une épaisseur comprise 60 µm et 130 µm.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce qu'un alliage Zn85Al15 est pulvérisé en tant que seconde couche.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que du cuivre est allié à la seconde couche.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que le procédé de pulvérisation gazodynamique à froid est utilisé pour la pulvérisation de la première couche et/ou de la seconde couche.
  13. Utilisation de cuivre ou d'un alliage à base de cuivre en tant que première couche à appliquer sur une chemise de cylindre en fonte grise, et utilisation d'un alliage zinc-aluminium composé de Zn avec une teneur pondérale d'aluminium comprise entre 3 et 20 %, en tant que seconde couche à appliquer sur la première couche.
EP06761655A 2005-06-15 2006-06-16 Procede pour munir une chemise de cylindre d'un revetement Not-in-force EP1896626B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005027828A DE102005027828A1 (de) 2005-06-15 2005-06-15 Verfahren zum Beschichten einer Zylinderlaufbuchse
PCT/DE2006/001023 WO2006133685A1 (fr) 2005-06-15 2006-06-16 Procede pour munir une chemise de cylindre d'un revetement

Publications (2)

Publication Number Publication Date
EP1896626A1 EP1896626A1 (fr) 2008-03-12
EP1896626B1 true EP1896626B1 (fr) 2009-09-09

Family

ID=36972883

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06761655A Not-in-force EP1896626B1 (fr) 2005-06-15 2006-06-16 Procede pour munir une chemise de cylindre d'un revetement

Country Status (9)

Country Link
US (1) US20090110841A1 (fr)
EP (1) EP1896626B1 (fr)
JP (1) JP5199868B2 (fr)
KR (1) KR101319165B1 (fr)
CN (1) CN101198712B (fr)
BR (1) BRPI0612058A2 (fr)
DE (2) DE102005027828A1 (fr)
RU (1) RU2414526C2 (fr)
WO (1) WO2006133685A1 (fr)

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CN102371351A (zh) * 2010-08-20 2012-03-14 宝馨实业股份有限公司 一种含高硅铝合金衬套及其制法
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Also Published As

Publication number Publication date
US20090110841A1 (en) 2009-04-30
CN101198712B (zh) 2010-12-15
DE502006004802D1 (de) 2009-10-22
RU2414526C2 (ru) 2011-03-20
JP5199868B2 (ja) 2013-05-15
JP2008544175A (ja) 2008-12-04
WO2006133685A1 (fr) 2006-12-21
KR101319165B1 (ko) 2013-10-16
RU2007147933A (ru) 2009-07-20
BRPI0612058A2 (pt) 2010-10-13
EP1896626A1 (fr) 2008-03-12
CN101198712A (zh) 2008-06-11
KR20080019202A (ko) 2008-03-03
DE102005027828A1 (de) 2006-12-21

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