WO2006133685A1 - Method for coating a cylinder sleeve - Google Patents

Method for coating a cylinder sleeve Download PDF

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Publication number
WO2006133685A1
WO2006133685A1 PCT/DE2006/001023 DE2006001023W WO2006133685A1 WO 2006133685 A1 WO2006133685 A1 WO 2006133685A1 DE 2006001023 W DE2006001023 W DE 2006001023W WO 2006133685 A1 WO2006133685 A1 WO 2006133685A1
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WO
WIPO (PCT)
Prior art keywords
layer
alloy
sprayed
cylinder
cylinder liner
Prior art date
Application number
PCT/DE2006/001023
Other languages
German (de)
French (fr)
Inventor
Gerhard Bucher
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
Priority to EP06761655A priority Critical patent/EP1896626B1/en
Priority to JP2008516123A priority patent/JP5199868B2/en
Priority to CN200680021287XA priority patent/CN101198712B/en
Priority to US11/921,692 priority patent/US20090110841A1/en
Priority to DE502006004802T priority patent/DE502006004802D1/en
Priority to BRPI0612058-0A priority patent/BRPI0612058A2/en
Priority to KR1020077025418A priority patent/KR101319165B1/en
Publication of WO2006133685A1 publication Critical patent/WO2006133685A1/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
    • 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.
  • 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 AISi 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 even an additional 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 coefficient of thermal expansion of the AISi cover layer is approximately 1.7 times the coefficient of thermal expansion of gray cast iron, so that, in the case of temperature changes, stresses arise in the known layer system which impair the bond between the cylinder liner and the cylinder crankcase.
  • 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 alloy 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, with both aluminum-based and magnesium-based castings 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 use the Ka Itgassp scribe method, wherein 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.
  • 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, causing the second layer to melt from its casting material as the cylinder crankcase is cast, thereby ensuring metallic bonding between the cylinder liner and the cylinder crankcase surround material 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 for the AlZn alloy to be a few wt%. Adding copper, because this the formation of the oxide layer is completely prevented, which brings a further improvement in the bond between the cylinder liner and the crankcase with it.

Abstract

The invention relates to a method for coating a cylinder sleeve consisting of an iron-based material. A first layer and a second layer made of a zinc alloy are injected onto the outer surface using a thermal injection method. A good metallic connection between the cylinder sleeve and the cylinder crankcase, wherein the cylinder sleeve is poured, is produced by using alloyed or unalloyed copper for the first layer and by using a zinc-aluminium-alloy for the second layer.

Description

Verfahren zum Beschichten einer Zylinderlaufbuchse Method for coating a cylinder liner
Die Erfindung betrifft ein Verfahren zum Beschichten einer Zylinderlaufbuchse nach dem Oberbegriff des Anspruches 1.The invention relates to a method for coating a cylinder liner according to the preamble of claim 1.
Zylinderkurbelgehäuse werden üblicherweise aus Leichtmetall, insbesondere aus Aluminium, gegossen, wobei wegen der schlechten tribologischen Eigenschaften der Leichtmetalle die Notwendligkeit besteht, Zylinderlaufbuchsen aus einem Eisenbasiswerkstoff, beispielsweise aus Grauguss, in das Zylinderkurbelgehäuse mit einzugießen. Hierbei ergeben sich die Probleme, die Zylinderlaufbuchsen ausreichend fest im Zylinderkurbelgehäuse zu verankern, und einen ausreichenden Wärmeübergang zwischen den Zylinderlaufbuchsen und dem Zylinderkurbelgehäuse zu gewährleisten. Diese Probleme können dadurch gelöst werden, dass die Außenflächen der Zylinderlaufbuchsen eine Rauhgussstruktur mit Hinterschnitten erhalten. Dies bringt aber mit sich, dass die Stege zwischen den in das Zylinderkurbelgehäuse eingegossenen Zylinderlaufbuchsen sehr breit sind, und dass deshalb der Platzbedarf der Zylinderlaufbuchsen sehr groß ist.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.
Im Rahmen des Trendes bei der Motorenentwicklung, die Motoren bei gleicher Leistung zu verkleinern, ergibt sich die Notwendigkeit, die Abstände zwischen den einzelnen Zylinderlaufbuchsen zu verringern und zudem die Wärmeabfuhr vom Brennraum über die Zylinderlaufbuchse zu den Kühlräumen des Zylinderkurbelgehäuses zu verbessern. Diese Probleme können dadurch gelöst werden, dass als Alternative zur Raugussbuchse Zylinderlaufbuchsen aus Grauguss mit einer glatten oder mäßig rauen Außenfläche und mit einer Beschichtung verwendet werden, die das Anbinden der Zylinderlaufbuchse an das Umgussmaterial des Zylinderkurbelgehäuses sicherstellt. Eine derartige Zylinderlaufbuchse aus Grauguss ist in der Patentschrift DE 197 29 017 C2 beschrieben. Diese weist auf ihrer Außenfläche eine im Flammspritzverfahren oder im Lichtbogenspritzverfahren aufgebrachte Deckschicht aus einer AISi-Legierung auf, die weniger als 15% Silizium enthält. Auf dieser Deckschicht ist eine Oxidationsschutzschicht aufgetragen, die aus einer Zinklegierung besteht, und deren Aufgabe es ist, das Oxidieren des AlSi-Schicht, wodurch die metallische Bindung der Deckschicht mit dem Umgussmaterial des Zylinderkurbelgehäuses verhindert wird, zu unterbinden.As part of the trend in engine development to reduce the size of the engines with the same power, there is a need to reduce the distances between the individual cylinder liners and also to improve the heat dissipation from the combustion chamber via the cylinder liner to the cooling chambers of the cylinder crankcase. These problems can be solved by using as an alternative to Raugussbuchse cylinder liners made of gray cast iron with a smooth or moderately rough outer surface and with a coating that ensures the attachment of the cylinder liner to the Umgussmaterial the cylinder crankcase. Such a cylinder liner made of gray cast iron is described in the patent DE 197 29 017 C2. This has on its outer surface applied by flame spraying or by arc spraying surface layer of an AISi 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.
Nachteilig ist hierbei, dass bereits beim Aufspritzen der Deckschicht die AISi-Legierung oxidiert. Die hierbei gebildete Oxidhaut haftet sehr fest auf der AlSi-Schicht. Zudem ist ihre Schmelztemperatur höher als die beim Umgießen erreichbaren Temperaturen. Mit viel Aufwand ist die Oxidhaut zwar entfernbar, sie bildet sich aber nach dem Entfernen sehr schnell wieder neu, sodass auch eine zusätzlich aufgebrachte Schutzschicht aus Zink oder aus einer Zink-Legierung eine metallische Bindung zwischen der AlSi-Schicht und dem Umgussmaterial des Zylinderkurbelgehäuses nicht sicherstellen kann.The disadvantage here is that the AISi alloy is already oxidized during the spraying of the cover layer. The resulting oxide skin adheres very firmly to the AlSi layer. In addition, their melting temperature is higher than the achievable temperatures during encapsulation. With much effort, the oxide skin is indeed removable, but it forms after removal very quickly again, so that even an additional 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.
Zudem ist der Wärmeausdehnungskoeffizient der AISi-Deckschicht ungefähr 1 , 7-mal so groß wie der Wärmeausdehnungskoeffizient von Grauguss, sodass sich bei Temperaturwechseln Spannungen im bekannten Schichtsystem ergeben, die die Bindung zwischen der Zylinderlaufbuchse und dem Zylinderkurbelgehäuse beeinträchtigen.In addition, the coefficient of thermal expansion of the AISi cover layer is approximately 1.7 times the coefficient of thermal expansion of gray cast iron, so that, in the case of temperature changes, stresses arise in the known layer system which impair the bond between the cylinder liner and the cylinder crankcase.
Diese Nachteile des Standes der Technik zu vermeiden, d.h., die metallische Bindung der Zylinderlaufbuchse mit dem Umgussmaterial des Zylinderkurbel-gehäuses und damit auch den Wärmeübergang zwischen der Zylinderlaufbuchse und dem Zylinderkurbelgehäuse zu verbessern, ist Aufgabe der Erfindung. Gelöst wird diese Aufgabe mit den im Kennzeichen des Hauptanspruches stehenden Merkmalen. Hierbθi ergeben sich die Vorteile, dass die Gradation der thermischen Ausdehnungskoeffizienten im erfindungsgemäßen Schichtaufbau zwischen der Graugussbuchse, dem Schichtsystem und dem Umgussmaterial des Zylinderkurbelgehäuses die thermisch bedingten Spannungen im Schichtaufbau gemäß der Erfindung erheblich reduziert. Zudem bewirkt die Gradation der Schmelztemperaturen ausgehend von der Zylinderlaufbuchse, über das erfindungsgemäße Schichtensystem bis hin zum Umgussmaterial des Zylinderkurbelgehäuses ein Anlösen beziehungsweise ein diffusionsbedingtes Anlegieren der äußeren Schicht mit dem Umgussmaterial, was eine stabile metallische Bindung zwischen der Zylinderlaufbuchse und dem Umgussmaterial des Zylinderkurbelgehäuses bewirkt. Letztlich hat die aus den erfindungsgemäßen Legierungen bestehende Beschichtung den Vorteil, dass sich ihre Legierungsbestandteile in der Bindungszone an der Ausscheidungshärtung beteiligen.To avoid these disadvantages of the prior art, ie, to improve the metallic bond of the cylinder liner with the surrounding material of the cylinder crankcase and thus also the heat transfer between the cylinder liner and the cylinder crankcase, is an object of the invention. This problem is solved with the features in the characterizing part of the main claim. Hierbθi there are the advantages that the gradation of thermal expansion coefficients in the layer structure of 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. In addition, 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. Finally, the coating consisting of the alloys according to the invention has the advantage that its alloy constituents participate in the precipitation hardening in the bonding zone.
Zweckmäßige Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche.Advantageous embodiments of the invention are the subject of the dependent claims.
Das erfindungsgemäße Verfahren zum Beschichten einer in ein Zylinderkurbelgehäuse einzugießenden Zylinderlauf buchse wird im Folgenden näher erläutert.The inventive method for coating a einzinkießenden in a cylinder crankcase cylinder liner will be explained in more detail below.
Verwendet wird hierzu eine Zylinderlaufbuchse, die aus einem Eisenbasiswerkstoff besteht, das legiert oder unlegiert sein kann. Vorzugsweise besteht die Zylinderlaufbuchse aus Grauguss, der entweder lamellares Graphit, Vermikulargraphit oder Kugelgraphit enthalten kann. Der Grauguss kann hierbei ein ferritisch-perlitisches, ein perlitisches, ein bainitisches oder ein austenitisches Grundgefüge aufweisen. Die Außenfläche der Zylinderlaufbuchse kann glatt ausgebildet sein. Sie kann aber auch alle weiteren Oberflächengüten bis hin zu einer flache Raugussoberfläche aufweisen. Darüberhinaus kann die Zylinderlaufbuchse eine spanend bearbeitete Außenfläche aufweisen.For this purpose, a cylinder liner is used, which consists of an iron-based material that may be alloyed or unalloyed. Preferably, 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 Raugussoberfläche. In addition, the cylinder liner may have a machined outer surface.
Zum Eingießen der Zylinderlaufbuchse in das Zylinderkurbelgehäuse können alle gebräuchlichen Gießverfahren, wie beispielsweise das Druckgießverfahren, das Pressgießverfahren, das Schwerkraftgießverfahren oder das Niederdruck-gießverfah- ren verwendet werden.For pouring the cylinder liner into the cylinder crankcase all common casting methods, such as die casting, the Press casting, the gravity casting or the low-pressure casting method are used.
Das Zylinderkurbelgehäuse besteht aus einem der gebräuchlichen Leichtmetall- Gusswerkstoff, wobei sowohl Gusswerkstoffe auf Aluminiumbasis als auch auf Magnesium-Basis in Frage kommen.The cylinder crankcase is made of one of the common light metal casting material, with both aluminum-based and magnesium-based castings in question.
Um beim Eingießen der Zylinderlaufbuchse in das Zylinderkurbelgehäuse die metallische Bindung der Zylinderlaufbuchse mit dem Umgussmaterial des Zylinderkurbelgehäuses sicherzustellen, wird die Außenfläche der Zylinderlaufbuchse durch thermisches Spritzen beschichtet. Als Vorbereitung hierfür ist es erforderlich, die Außenfläche von Schmutz und Oxiden zu säubern und anschließend aufzurauen. Geeignete Verfahren hierzu sind das Bürsten und/oder das Strahlen. Hierzu eignet sich insbesondere das Strahlen mit grobem Korund, d.h., mit kristallisiertem AI2O3.In order to ensure the metallic bond of the cylinder liner with the Umgussmaterial the cylinder crankcase when pouring the cylinder liner into the cylinder crankcase, 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.
Unmittelbar im Anschluss daran wird auf die Außenfläche der Zylinderlaufbuchse durch thermisches Spritzen eine erste Schicht aufgetragen. Diese erste Schicht besteht entweder aus 99,9%igem Kupfer, aus einer CuAI8-Legierung, aus einer CuAI8Ni2-Legierung, aus einer CuP8-Legierung, aus einer CuSi3-Legierung oder aus einer CuZn37-Legierung (Messing). Angestrebt wird hierbei eine poren- und oxidarme Schicht mit einer Dicke zwischen 60μm und 130μm.Immediately thereafter, 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 60μm and 130μm.
Zur Verfeinerung der Gradation der Schmelztemperaturen der auf die Zylinderlaufbuchse aufgetragenen Schichten ist es vorteilhaft, auf eine erste aus reinem Kupfer bestehende Schicht eine weitere Schicht aus einer der vorgenannten Kupferlegierung aufzutragen, deren Schmelztemperatur geringer ist als diejenige von Kupfer, deren Schmelztemperatur aber höher ist, als diejenige des Materials, aus dem die im Folgenden als zweite Schicht bezeichnete äußere Beschichtung besteht.To refine the gradation of the melting temperatures of the layers applied to the cylinder liner, it is advantageous to apply to a first pure copper layer 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.
Da Drähte aus den genannten Legierungen im Handel erhältlich ist, wird als thermisches Spritzverfahren bevorzugt das Drahtflammspritzen angewandt, wobei der drahtförmige Spritzzusatzwerkstoff im Zentrum einer Actylen-Sauerstoffflamme geschmolzen und mit Hilfe eines Zerstäubergases, wie beispielsweise Druckluft oder Stickstoff, auf die Außenfläche der Zylinderlaufbuchse gespritzt wird.Since 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.
Geeignet ist auch das Lichtbogen-Drahtspritzen, wobei zwei drahtförmige Spritzzusätze in einem Lichtbogen geschmolzen und mittels eines Zerstäubergases auf die Außenfläche der Zylinderlaufbuchse geschleudert werden. Hierbei besteht die Möglichkeit, zwei in ihrer Zusammensetzung unterschiedliche Drähte miteinander abzuschmelzen, wobei die Zusammensetzung der dadurch erzeugten Schicht in weiten Bereichen variiert werden kann. Werden beispielsweise Kupfer- und Zinkdraht verwendet, besteht die Möglichkeit, eine CuZn-Legierung mit bis zu 45% Zink auf die Außenfläche der Zylinderlaufbuchse aufzutragen. Bei einer Verwendung von Stickstoff oder Argon als Zerstäubergas wird eine Oxidation der Materialien weitgehend unterbunden.Also suitable is the 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. In this case, it is possible to melt two different wires in their composition with each other, wherein the composition of the layer produced thereby can be varied within wide ranges. If, for example, copper and zinc wire are used, it is possible to apply a CuZn alloy with up to 45% zinc to the outer surface of the cylinder liner. When using nitrogen or argon as a sputtering gas oxidation of the materials is largely prevented.
Eine Möglichkeit, die Oxydation des Spritzwerkstoffes und den Oxidgehalt der aufgespritzten Schicht weiter zu verringern, besteht darin, das Ka Itgassp ritzverfahren anzuwenden, wobei ungeschmolzene und nur auf wenige hundert Grad erwärmte Pulverpartikel auf eine Geschwingkeit zwischen 300m/sec. und 1200 m/sec. beschleunigt und auf die Außenfläche der Zylinderlaufbuchse gespritzt werden. Durch Mikroreibung aufgrund des Aufpralls der Pulverteilchen steigt die Temperatur an der Berührungsfläche und führt zu Mikroverschweißungen der Pulverpartikel mit der Außenfläche der Zylinderlaufbuchse.One way to further reduce the oxidation of the sprayed material and the oxide content of the sprayed layer is to use the Ka Itgassp scribe method, wherein 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.
Anwendbar ist auch das Hochgeschwindigkeits-Flammspritzen (HVOF-Spritzen), wobei eine kontinuierliche Gasverbrennung mit hohen Drücken innerhalb einer Brennkammer erfolgt, in deren zentraler Achse der pulverförmige Spritzzusatz zugeführt wird. Der in der Brennkammer erzeugte hohe Druck des Brenngas-Sauerstoff- Gemisches erzeugt eine hohe Partikelgeschwindigkeit, die zu sehr dichten Spritzschichten mit guten Hafteigenschaften führt. Diθ Funktionen der ersten Schicht bestehen darin, eine gute Haftung der ersten Schicht auf dem Grauguss der Zylinderlaufbuchse sicherzustellen, gute Bindungsvoraussetzungen für eine zweite Schicht zu schaffen, und eine Gradation der Schmelztemperaturen, d.h., einen stufenweisen Übergang der Schmelztemperaturen des Graugusses der Zylinderlaufbuchse, über die erste Schicht und die zweite Schicht bis hin zum Umgussmetall des Zylinderkurbelgehäuses zu realisieren. Zudem wird hierdurch eine Gradation der Wärmeausdehnungskoeffizienten ausgehend von der Zylinderlaufbuchse über die erste und die zweite Schicht bis hin zum Leichtmetall des Zylinderkurbelgehäuses herbeigeführt.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. 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.
Um ein Oxidieren der ersten Schicht zu vermeiden, wird unmittelbar nach dem Aufbringen der ersten Schicht die zweite Schicht unter Anwendung eines der oben erwähnten, thermischen Spritzverfahrens auf die erste Schicht aufgetragen. Bevorzugt wird hierzu ein Zn85AI15-Legierung mit 85% Zink und 15% Aluminium verwendet. Bei dieser Legierung kann der Aluminiumgehalt aber auch zwischen 3% und 20% variieren. Angestrebt wird eine poren- und oxidarme Schicht mit einer Dicke zwischen 60μm und 130μm.In order to avoid oxidation of the first layer, immediately after the application of the first layer, the second layer is applied to the first layer using one of the above-mentioned thermal spraying methods. For this purpose, a Zn85Al15 alloy with 85% zinc and 15% aluminum is preferably used. However, in this alloy, 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.
Die Funktion der zweiten Schicht besteht darin, auf der ersten Schicht gut zu haften. Zudem hat die AlZn-Legierung mit 15 Gew.% Aluminium einen Schmelzpunkt von 450°C, wodurch bewirkt wird, dass die zweite Schicht beim Gießen des Zylinderkurbelgehäuses von dessem Umgussmaterial angeschmolzen wird, wodurch die metallische Bindung zwischen der Zylinderlaufbuchse und dem Umgussmaterial des Zylinderkurbelgehäuses sichergestellt wird.The function of the second layer is to adhere well to the first layer. In addition, the 15 wt.% Aluminum AlZn alloy has a melting point of 450 ° C, causing the second layer to melt from its casting material as the cylinder crankcase is cast, thereby ensuring metallic bonding between the cylinder liner and the cylinder crankcase surround material becomes.
Hierbei bildet die AlZn-Legierung zwar eine sehr dünne Oxidschicht, die die Bindung Zylinderlaufbuchse-Kurbelgehäuse aber nicht behindert. Dennoch ist es vorteilhaft, der AlZn-Legierung einige Gew.%. Kupfer hinzuzulegieren, denn dadurch wird die Bildung der Oxidschicht vollständig verhindert, was eine weitere Verbesserung der Bindung zwischen Zylinderlaufbuchse und Kurbelgehäuse mit sich bringt. Although the AlZn alloy forms a very thin oxide layer, this does not hinder the bond between cylinder liner and crankcase. Nevertheless, it is advantageous for the AlZn alloy to be a few wt%. Adding copper, because this the formation of the oxide layer is completely prevented, which brings a further improvement in the bond between the cylinder liner and the crankcase with it.

Claims

Patentansprüche claims
1. Verfahren zum Beschichten einer Zylinderlaufbuchse aus einem Eisenbasiswerkstoff, wobei unter Anwendung eines thermischen Spritzverfahrens auf die Außenfläche der Zylinderlaufbuchse eine erste Schicht und eine zweite Schicht aus einer Zinklegierung aufgespritzt werden, gekennzeichnet durch die folgenden Verfahrensschritte,A method of coating a cylinder liner of an iron-based material, wherein a first layer and a second layer of a zinc alloy are sprayed onto the outer surface of the cylinder liner using a thermal spray process, characterized by the following process steps,
- Aufspritzen von Kupfer oder von einer Kupfer-Basis-Legierung auf die Außenfläche der Zylinderlaufbuchse als erste Schicht, und- Spraying copper or a copper-based alloy on the outer surface of the cylinder liner as the first layer, and
- Aufspritzen einer Zink-Aluminium-Legierung auf die erste Schicht als zweite Schicht.- Spraying a zinc-aluminum alloy on the first layer as a second layer.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als erste Schicht 99,9%iges Kupfer aufgespritzt wird.2. The method according to claim 1, characterized in that is sprayed as the first layer of 99.9% copper.
3. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als erste Schicht eine CuAI8-Legierung aufgespritzt wird.3. The method according to claim 1, characterized in that as the first layer, a CuAl8 alloy is sprayed.
4. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als erste Schicht eine Cu AI8Ni2-Legierung aufgespritzt wird.4. The method according to claim 1, characterized in that as a first layer, a Cu Al8Ni2 alloy is sprayed.
5. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als erste Schicht eine CuP8-Legierung aufgespritzt wird.5. The method according to claim 1, characterized in that as a first layer, a CuP8 alloy is sprayed.
6. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als erste Schicht eine CuSi3-Legierung aufgespritzt wird.6. The method according to claim 1, characterized in that a CuSi3 alloy is sprayed as the first layer.
7. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als erste Schicht eine CuZn-Legierung mit bis zu 45 Gew. % Zink aufgespritzt wird. 7. The method according to claim 1, characterized in that is sprayed as the first layer, a CuZn alloy with up to 45 wt.% Zinc.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass als erste Schicht eine CuZn37-Legierung aufgespritzt wird.8. The method according to claim 7, characterized in that is sprayed as a first layer, a CuZn37 alloy.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die erste Schicht eine Dicke zwischen 60μm und 130μm aufweist.9. The method according to any one of claims 1 to 8, characterized in that the first layer has a thickness between 60μm and 130μm.
10. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als 2. Schicht eine ZnAI-Legierung mit 3 bis 20 Gew.% Aluminium aufgespritzt wird.10. The method according to claim 1, characterized in that as the second layer, a ZnAl alloy is sprayed with 3 to 20 wt.% Aluminum.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass als 2. Schicht eine Zn85AI15-Legierung aufgespritzt wird.11. The method according to claim 10, characterized in that a Zn85AI15 alloy is sprayed as the 2nd layer.
12. Verfahren nach Anspruch 10 oder 11 , dadurch gekennzeichnet, dass der 2. Schicht Kupfer hinzulegiert wird.12. The method according to claim 10 or 11, characterized in that the second layer of copper is added.
13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass zum Aufspritzen der 1. und/oder der 2. Schicht das Kaltgasspritzverfahren verwendet wird.13. The method according to any one of claims 1 to 12, characterized in that for spraying the 1st and / or the 2nd layer, the cold gas spraying method is used.
14. Verwendung von Kupfer oder von einer Kupferbasislegierung als erste auf eine Zylinderlaufbuchse aus Grauguss aufzutragende Schicht, und Verwendung einer Zink-Aluminium-Legierung als zweite auf die erste Schicht aufzutragende Schicht. 14. Use of copper or of a copper-based alloy as the first layer to be applied to a cylinder liner of gray cast iron, and use of a zinc-aluminum alloy as the second layer to be applied to the first layer.
PCT/DE2006/001023 2005-06-15 2006-06-16 Method for coating a cylinder sleeve WO2006133685A1 (en)

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EP06761655A EP1896626B1 (en) 2005-06-15 2006-06-16 Method for coating a cylinder sleeve
JP2008516123A JP5199868B2 (en) 2005-06-15 2006-06-16 How to coat a cylinder sleeve
CN200680021287XA CN101198712B (en) 2005-06-15 2006-06-16 Method for coating a cylinder sleeve
US11/921,692 US20090110841A1 (en) 2005-06-15 2006-06-16 Method for coating a cylinder sleeve
DE502006004802T DE502006004802D1 (en) 2005-06-15 2006-06-16 METHOD FOR COATING A CYLINDER BUSHING
BRPI0612058-0A BRPI0612058A2 (en) 2005-06-15 2006-06-16 process for coating a cylinder liner
KR1020077025418A KR101319165B1 (en) 2005-06-15 2006-06-16 Method for coating a cylinder sleeve

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