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EP1322794A2 - Thermally applied coating for piston rings, consisting of mechanically alloyed powders - Google Patents

Thermally applied coating for piston rings, consisting of mechanically alloyed powders

Info

Publication number
EP1322794A2
EP1322794A2 EP01976101A EP01976101A EP1322794A2 EP 1322794 A2 EP1322794 A2 EP 1322794A2 EP 01976101 A EP01976101 A EP 01976101A EP 01976101 A EP01976101 A EP 01976101A EP 1322794 A2 EP1322794 A2 EP 1322794A2
Authority
EP
European Patent Office
Prior art keywords
wear
resistant coating
coating according
metallic matrix
powders
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.)
Granted
Application number
EP01976101A
Other languages
German (de)
French (fr)
Other versions
EP1322794B1 (en
Inventor
Christian Herbst-Dederichs
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.)
Federal Mogul Burscheid GmbH
Original Assignee
Federal Mogul Burscheid 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
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Application filed by Federal Mogul Burscheid GmbH filed Critical Federal Mogul Burscheid GmbH
Publication of EP1322794A2 publication Critical patent/EP1322794A2/en
Application granted granted Critical
Publication of EP1322794B1 publication Critical patent/EP1322794B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/937—Sprayed metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49229—Prime mover or fluid pump making
    • Y10T29/49274—Piston ring or piston packing making
    • Y10T29/49281—Piston ring or piston packing making including coating or plating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/1216—Continuous interengaged phases of plural metals, or oriented fiber containing
    • Y10T428/12174—Mo or W containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component

Definitions

  • the present invention relates to a wear-resistant coating for use for running surfaces and flanks of piston rings in internal combustion engines.
  • the wear-resistant coating according to the invention is obtained by mechanical alloying of powders which form a metallic matrix with hard and lubricant dispersoids.
  • the coating is then thermally applied to the workpieces, in particular by means of high-speed flame spraying (HVOF).
  • HVOF high-speed flame spraying
  • the workpieces are the running surfaces and flank parts of piston rings in internal combustion engines.
  • the invention is therefore particularly concerned with the production and composition of coatings of mechanically alloyed powders with tribologically optimal properties as starting materials for the purpose of coating piston ring running surfaces by means of thermal processes, e.g. by means of thermal spraying and with the coatings formed from the powders mentioned on e.g. Piston rings of internal combustion engines.
  • Piston rings are subject to constant sliding wear due to their constant engagement with the cylinder race. This manifests itself in abrasive abrasion of the piston ring surface or its coating as well as partial transfer of material from the cylinder running surface to the piston ring running surface and vice versa. With adapted coatings it is possible to reduce these negative influences. Paricle-reinforced hard chrome coatings show significantly better abrasion resistance than uncoated or nitrided rings (see EP 217126 B1), but also as conventional hard chrome coatings and plasma spray coatings based on molybdenum. Nevertheless, due to the increasing pressure and temperature parameters in modern internal combustion engines, these coatings also reach the limit of their performance.
  • Ceramics can also be applied directly to piston rings using various coating processes. So you can e.g. can be deposited directly by vapor deposition (PVD or CVD). The disadvantage here is that the order performance for this application is far too low and therefore uneconomical.
  • Plasma spraying leads to relatively high application rates, but these coatings are usually under tensile stress, which means that they are prone to cracking and breakout. This is reinforced above all by the very brittle nature of the ceramics themselves.
  • Nanocrystalline hard metals 1 to 100 nm
  • nano-carbide reinforced materials were processed into layers using vacuum plasma spraying technology. With a comparatively lower proportion of hard material, higher hardness can be achieved in the layers produced using this method.
  • the coatings show a significantly higher ductility and thus impact resistance than conventionally reinforced materials. But only with the help of high-speed flame spraying technology is it possible to map powder morphologies in the layer.
  • Nano-oxidically reinforced metals should therefore primarily be sprayed using high-speed flame spraying (HVOF).
  • HVOF high-speed flame spraying
  • This process is particularly interesting for thermal wettable powders because it leads to a number of special powder properties.
  • the crushing and grinding process on the powder surfaces constantly increases the density of stacking defects, defects and dislocations, while the grain sizes can be reduced to nanocrystalline dimensions.
  • These permanently fresh surfaces are characterized by high activity, so that oxide-metal and carbide-metal connections of high strength can also be created.
  • Powdered hard metals WC-Co
  • cermets NiCr-CrC
  • thermal coating processes The basis for this is either a powder mixture or a composite powder.
  • mechanical mixtures generally provide the lowest layer qualities, since the bond is only formed in the coating process and the hard materials have to be relatively large due to the required flow properties.
  • Compound powders are usually produced by agglomeration into so-called micropellets.
  • microfine starting powders become processable in a spray drying process, i.e. primarily processed free-flowing powders. In order to increase the strength of the agglomerate or to achieve certain agglomerate densities, these are usually sintered.
  • composite powder production is to mix the components with subsequent sintering to form a block.
  • the powder is obtained here by breaking and grinding the block.
  • composite powders are made by coating, for example a hard material powder is chemically or physically coated by a metallic element, or so-called cladding - fine metal powders are glued to the hard material core in a spray drying process.
  • a disadvantage of the required sintering is that on the one hand the economy of the powder is reduced, and on the other hand a sinterability of the starting components is required. This is particularly the case with the WC-Co combination, but is not available with the combination of, for example, metallic binder and oxide-ceramic hard materials, which is interesting from an economic and tribological point of view. Therefore, such powders have so far not been successfully used for the thermal coating of piston ring running surfaces.
  • An approach to the thermal coating of metal parts, such as piston rings and cylinder liners, is described in DE 197 00 835 AI.
  • the composite powder used in this document is a mixture of carbides, metal powder and solid lubricants that is processed into a self-lubricating composite layer using a high-speed flame spraying process.
  • the composite particles made of CrC and ⁇ iCr are mixed with the solid lubricants.
  • a disadvantage of this type of production of the composite powder according to DE 197 00 835 AI is that in order to obtain the necessary flowability, as a condition for processing in the high-speed flame spraying process, relatively coarse particles have to be formed.
  • the grain size of the solid lubricant article must be> 20 ⁇ m so that the composite powder has the flowability required for spraying in the high-speed flame spraying process.
  • These coarse particles cause a concentrated accumulation of solid lubricant phases in the coating, which in turn has a negative effect on wear, since the coarse and thus also relatively large solid lubricant areas can break out and are only available selectively due to their size as a lubricant.
  • this object is achieved by the coating according to claim 1 and by the piston ring according to claim 11.
  • the starting powders are therefore alloyed mechanically, in particular in attritors, hammer mills or ball mills.
  • starting powders are broken down and kneaded into one another at the same time, so that a composite powder is formed even without sintering.
  • combinations of materials such as metals and oxides that are not suitable for sintering can be processed to composite powders.
  • This technology is used, for example, on an industrial scale to produce so-called ODS alloys for high-temperature applications, where about 2% by weight of oxides comminuted to the nanodimension are added to the metallic matrix.
  • the invention therefore relates to the production of mechanically alloyed powders and the use of these powders by means of thermal coating processes for the purpose of coating the tread and flanks of piston rings and piston ring coatings produced therefrom.
  • the starting powders used according to the invention have a suitable particle size. For thermal spraying, grain sizes of 5-80 ⁇ m, particularly preferably 5-60 ⁇ m, are preferably used.
  • the starting powder consists of a metallic matrix and at least one ceramic phase to increase the wear resistance of the metallic matrix.
  • the ceramic phases in the starting powder or in the finished coating have diameters of ⁇ 10 ⁇ m. They preferably have size ranges from a few nanometers to a few micrometers.
  • the metallic matrix of the starting powder and the coating comprise in particular alloys based on iron, nickel, chromium, cobalt, molybdenum.
  • the starting powder can consist of a metallic matrix and at least one solid lubricant to improve the lubricating properties of the matrix.
  • the solid lubricant phase in the starting powder has grain sizes ⁇ 20 ⁇ m, preferably ⁇ 10 ⁇ m.
  • solid lubricant particles for example, those made of graphite, hexagonal boron nitride or polytetrafluoroethylene can be used.
  • Another advantage of the material according to the invention compared to DE 197 00 835 AI is that the dispersoids and solid lubricants grind to a composite powder, i. H. mechanically alloyed. In this way, very fine composite particles can be generated, which in turn are found in the layer as finely distributed solid lubricant phases. These finely distributed solid lubricant phases now enable optimal and even distribution of the lubricants, which reduces wear on the layer.
  • hard material particles for example from the group of tungsten carbide, chromium carbide, aluminum oxide, silicon carbide, boron carbide, titanium carbide and / or diamond, into the material according to the invention.
  • composite powders such as metal + oxide ceramic and Metal + diamond can be produced for subsequent coating processing using thermal processes.
  • the hard material contents in the metal matrix can be well over 50% by volume, which means that the properties of the hard material phases can be used much better than the low contents achieved today, for example, with galvanic chromium dispersion layers.
  • virtually arbitrarily fine and homogeneously distributed hard material phases can be generated in the metal matrix of any composition. In this way, the matrix can be specifically optimized for resistance to abrasion and burn marks, and a certain proportion of larger hard phases can perform purely tribological tasks.
  • the starting materials are filled into the mill and the grinding process is started.
  • the powders are broken or deformed by impact processes, which are generated either by the balls contained in the mixer or by contact with the chamber walls, depending on the deformability.
  • ceramics that have no deformability are continuously broken down.
  • the metallic matrix experiences significant increases in strength when the ceramic phases contained in it fall below the one-micron limit.
  • metals with deformability are largely only deformed, but sometimes also broken by embrittling work hardening.
  • the broken hard material phases are alloyed into the metal matrix and kneaded into processable powder fractions by the continuous grinding movement.
  • the ceramic breaking process continuously produces fresh, high-energy surfaces which have a high microscopic affinity. Due to the high mechanical impulses during milling, the metallic and ceramic surfaces are pressed together so strongly that interface reactions probably occur at the atomic level. Subsequent sintering of the powders can, in individual cases, further increase the ceramic-metal cohesion.
  • the hard material sizes in the powder can be set in a targeted manner.
  • a hard material phase and a metal matrix can serve as starting materials, but practically any number.
  • a proportion of solid lubricants useful for the application can also be added to the powder.
  • the powders are then applied by thermal coating processes, in particular thermal spraying, laser coating and hardfacing and soldering can be used.
  • HVOF high-speed flame spraying
  • Example 1 conventional wettable powder of aluminum oxide was ground with a conventional NiCr wettable powder in a volume ratio of 1: 1. After the grinding process, a powder of finely distributed aluminum oxide phases (gray) was created in the matrix (Figure 1: mechanically alloyed powder NiCr-34Al 2 O 3 ). After processing with HVOF, a very well adhering, dense coating is created, which has the same microstructure as the powder ( Figure 2: HVOF-sprayed layer shows identical microstructures).
  • Example 2 up to 20 vol.% Of a powdered solid lubricant was added to the powder from Example 1, which is demonstrably present in the layer after processing by means of HVOF and clearly improves the friction behavior of the layer on the piston ring.
  • Example 3 the matrix from Example 1 was further metallic elements such as Mo alloyed to improve the tribological properties of the piston ring coating.
  • the Mo powder is only slightly finely ground in the grinding process because of its high toughness, but is present in the powder and in the coating as a homogeneously distributed, excellently embedded phase.
  • the fire trace behavior of the Kolbeming coating was demonstrably improved in this way.
  • Example 4 50% by volume of two different ceramic phases (aluminum oxide, zirconium oxide) were added to the powder from Example 1.
  • the ceramics were added to the grinding process at different times, which means that the different ceramic phases in the HVOF layer have different fractions. This procedure allows one ceramic to control the matrix hardness in a targeted manner without adversely affecting the tribologically required hard phase size of the other ceramic. This clearly improves the abrasion resistance of the Kolbeming coating.
  • Example 5 the finest diamond dust was admixed and alloyed into a commercial NiCr wettable powder. After processing with HVOF, an increase in wear resistance compared to the unalloyed matrix was found, which has an advantageous effect on the tribological properties of the Kolbeming coating.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Powder Metallurgy (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

The invention relates to a wear-resistant coating used for bearing surfaces and flanks of piston rings in internal combustion engines. The wear-resistant inventive coating is obtained by mechanically alloying powders which form a metallic matrix with hard material dispersoids and lubricant material dispersoids. The coating is then thermally applied to the workpieces, especially by means of high velocity oxygen fuel spraying (HVOF). The workpieces coated are bearing surfaces and parts of flanks pertaining to piston rings in internal combustion engines.

Description

Titel: Thermisch aufgetragene Beschichtung für Kolbenringe aus mechanisch legierten Pulvern Title: Thermally applied coating for piston rings made of mechanically alloyed powders

Beschreibungdescription

Die vorliegende Erfindung betrifft eine verschleißfeste Beschichtung zur Verwendung für Laufflächen und Flanken von Kolbenringen in Verbrennungskraftmaschinen. Die erfindungsgemäße verschleißfeste Beschichtung wird erhalten durch mechanisches Legieren von Pulvern, die eine metallische Matrix bilden mit Hart- sowie Gleitstoffdispersoiden. Die Beschichtung wird thermisch dann auf die Werkstücke, insbesondere mittels Hochgeschwindigkeits-Flammspritzen (HVOF), aufgetragen. Bei den Werkstücken handelt es sich um die Laufflächen und Flankenteile von Kolbenringen in Verbrennungskraftmaschinen.The present invention relates to a wear-resistant coating for use for running surfaces and flanks of piston rings in internal combustion engines. The wear-resistant coating according to the invention is obtained by mechanical alloying of powders which form a metallic matrix with hard and lubricant dispersoids. The coating is then thermally applied to the workpieces, in particular by means of high-speed flame spraying (HVOF). The workpieces are the running surfaces and flank parts of piston rings in internal combustion engines.

Die Erfindung befaßt sich daher insbesondere mit der Herstellung und der Zusammensetzung von Beschichtungen mechanisch legierter Pulver mit tribologisch optimalen Eigenschaften als Ausgangsstoffe zum Zweck der Beschichtung von Kolbenringlaufflächen mittels thermischer Verfahren z.B. mittels dem thermischen Spritzen sowie mit den aus den erwähnten Pulvern entstehenden Beschichtungen auf z.B. Kolbenringen von Verbrennungskraftmaschinen.The invention is therefore particularly concerned with the production and composition of coatings of mechanically alloyed powders with tribologically optimal properties as starting materials for the purpose of coating piston ring running surfaces by means of thermal processes, e.g. by means of thermal spraying and with the coatings formed from the powders mentioned on e.g. Piston rings of internal combustion engines.

Kolbenringe unterliegen durch ihren ständigen Eingriff an der Zylinderlaufbahn einem ständigen Gleitverschleiß. Dieser äußert sich sowohl in abrasivem Abrieb der Kolbenringoberfläche oder seiner Beschichtung als auch teilweisem Übertrag von Material von der Zylinderlauffläche auf die Kolbenringlauffläche und umgekehrt. Durch angepaßte Beschichtungen ist es möglich, diese negativen Einflüsse zu verringern. So zeigen parikelverstärkte Hartchrombeschichtungen eine deutlich bessere Abriebfestigkeit als unbeschichtete oder nitrierte Ringe (siehe EP 217126 Bl), aber auch als konventionelle Hartchromschichten sowie Plasmaspritzschichten auf Molybdän-Basis. Dennoch geraten auch diese Beschichtungen aufgrund der steigenden Druck- und Temperaturparameter in modernen Verbrennungsmotoren in den Grenzbereich ihrer Leistungsfähigkeit. Daher werden neue Beschichtungen erforderlich, die über noch geringeren Abrieb und höhere Adhäsionsfestigkeit gegenüber den heute existierenden verfügen. Keramiken sind als Werkstoffe prinzipiell geeignet, diese Aufgabe zu erfüllen. Sie verfügen über eine ausgezeichnete Abriebfestigkeit und aufgrund ihres nichtmetallischen Bindungscharakters über eine sehr geringe Adhäsionsneigung gegenüber Metallegierungen.Piston rings are subject to constant sliding wear due to their constant engagement with the cylinder race. This manifests itself in abrasive abrasion of the piston ring surface or its coating as well as partial transfer of material from the cylinder running surface to the piston ring running surface and vice versa. With adapted coatings it is possible to reduce these negative influences. Paricle-reinforced hard chrome coatings show significantly better abrasion resistance than uncoated or nitrided rings (see EP 217126 B1), but also as conventional hard chrome coatings and plasma spray coatings based on molybdenum. Nevertheless, due to the increasing pressure and temperature parameters in modern internal combustion engines, these coatings also reach the limit of their performance. Therefore, new coatings are required that have even less abrasion and higher adhesive strength compared to the existing ones. In principle, ceramics are suitable as materials to fulfill this task. You have one excellent abrasion resistance and, due to their non-metallic binding character, a very low tendency to adhere to metal alloys.

Keramiken können durch verschiedene Beschichtungsverfahren direkt auch auf Kolbenringe aufgetragen werden. So können sie z.B. durch Aufdampfverfahren (PVD oder CVD) direkt abgeschieden werden. Nachteilig hierbei ist, daß die Auftragsleistungen für diese Anwendung viel zu niedrig und dementsprechend unwirtschaftlich sind.Ceramics can also be applied directly to piston rings using various coating processes. So you can e.g. can be deposited directly by vapor deposition (PVD or CVD). The disadvantage here is that the order performance for this application is far too low and therefore uneconomical.

Das Plasmaspritzen hingegen führt zu relativ hohen Auftragsleistungen, jedoch stehen diese Beschichtungen in der Regel unter Zugspannungen, wodurch sie riß- und ausbruchgefährdet sind. Dies wird vor allem auch durch den sehr spröden Charakter der Keramiken selbst verstärkt.Plasma spraying, on the other hand, leads to relatively high application rates, but these coatings are usually under tensile stress, which means that they are prone to cracking and breakout. This is reinforced above all by the very brittle nature of the ceramics themselves.

Die thermische Spritztechnik nimmt die positiven Erfahrungen mit nanokristallinen Hartmetallen (nanokristallin=l bis lOOnm) zunehmend auf. Schon bereits Ende der achtziger Jahre wurden nano-Karbid verstärkte Werkstoffe durch Vakuum-Plasmaspritztechnik zu Schichten verarbeitet. Bei vergleichbar geringeren Hartstoffanteilen können mit diesem Verfahren höhere Härten in den erzeugten Schichten erreicht werden. Die Beschichtungen zeigen eine deutlich höhere Duktilität und damit Schlagfestigkeit als konventionell verstärkte Werkstoffe. Aber erst mit Hilfe der Hochgeschwindigkeitsflammspritztechnik ist es möglich, Pulvermorphologien auch in der Schicht abzubilden. Nano-oxidisch verstärkte Metalle sollten daher vorrangig mittels Hochgeschwindigkeits-Flammspritzen (HVOF) verspritzt werden. Die Spritzpulver werden mittels Hochenergie-Mahlen hergestellt. Für thermische Spritzpulver ist dieser Prozeß besonders interessant, da er zu einer Reihe besonderer Pulvereigenschaften führt. So wird durch den Brech- und Mahlprozeß an den Pulveroberflächen ständig die Dichte an Stapelfehlern, Fehlstellen und Versetzungen erhöht, während die Korngrößen bis auf nanokristalline Dimensionen reduziert werden können. Diese permanent frisch entstehenden Oberflächen zeichnen sich durch eine hohe Aktivität aus, so daß auch Oxid-Metall- und Karbid-Metall- Verbindungen hoher Festigkeit entstehen können.Thermal spraying technology is increasingly taking up positive experiences with nanocrystalline hard metals (nanocrystalline = 1 to 100 nm). Already at the end of the eighties, nano-carbide reinforced materials were processed into layers using vacuum plasma spraying technology. With a comparatively lower proportion of hard material, higher hardness can be achieved in the layers produced using this method. The coatings show a significantly higher ductility and thus impact resistance than conventionally reinforced materials. But only with the help of high-speed flame spraying technology is it possible to map powder morphologies in the layer. Nano-oxidically reinforced metals should therefore primarily be sprayed using high-speed flame spraying (HVOF). The wettable powders are produced using high-energy grinding. This process is particularly interesting for thermal wettable powders because it leads to a number of special powder properties. The crushing and grinding process on the powder surfaces constantly increases the density of stacking defects, defects and dislocations, while the grain sizes can be reduced to nanocrystalline dimensions. These permanently fresh surfaces are characterized by high activity, so that oxide-metal and carbide-metal connections of high strength can also be created.

Wünschenswert ist es daher, die guten tribologischen Eigenschaften von Keramik mit den guten mechanischen Eigenschaften von Metallen zu verbinden. Denkbar ist z.B., Keramikpartikel in eine metallische Matrix einzulassen, wodurch eine duktile und zähe Bindung der harten und teilweise spröden Keramikpartikel gewährleistet ist. Die Keramikpartikel können dann bei geeigneter Freilegung an der Oberfläche die tribologischen Aufgaben übernehmen, während die Metallmatrix die mechanischen Lasten aufnimmt und gegebenenfalls Spannungen über Verformungen abbaut.It is therefore desirable to combine the good tribological properties of ceramics with the good mechanical properties of metals. It is conceivable, for example, to let ceramic particles into a metallic matrix, which ensures ductile and tough bonding of the hard and sometimes brittle ceramic particles. The ceramic particles can then take over the tribological tasks with suitable exposure on the surface, while the metal matrix absorbs the mechanical loads and if necessary, reduces stresses via deformations.

Ein solches Verbundprinzip wird heute bereits verwirklicht. So können z.B. pulverförmige Hartmetalle (WC-Co) oder Cermets (NiCr-CrC) mittels thermischer Beschichtungsverfahren zu Schichten verarbeitet werden. Grundlage hierfür ist entweder eine Pulvermischung oder ein Verbundpulver. Mechanische Mischungen liefern aber in aller Regel die niedrigsten Schichtqualitäten, da die Verbundbildung hierbei erst im Beschichtungsprozeß erfolgt und die Hartstoffe aufgrund ihrer geforderten Rieselfähigkeit relativ groß sein müssen. Verbundpulver werden in aller Regel durch Agglomeration zu sogenannten Mikropellets hergestellt. Hierbei werden mikrofeine Ausgangspulver in einem Sprühtrocknungsprozeß zu verarbeitungsfähigen, d.h. in erster Linie rieselfähigen Pulvern verarbeitet. Um die Festigkeit des Agglomerats zu erhöhen bzw. bestimmte Agglomeratsdichten zu erreichen, werden diese in aller Regel anschließend gesintert. Eine andere Möglichkeit der Verbundpulverherstellung ist das Vermischen der Komponenten mit anschließender Sinterung zum Block. Das Pulver wird hier durch Brechen und Mahlen des Blocks gewonnen. Des weiteren werden Verbundpulver durch Umhüllen, hierbei wird z.B. ein Hartstoffpulver durch ein metallisches Element chemisch oder physikalisch beschichtet, oder sogenanntes Cladding - dabei werden feine Metallpulver auf den Hartstoffkern im Sprühtrocknungsverfahren aufgeklebt - hergestellt.Such a network principle is already being implemented today. For example, Powdered hard metals (WC-Co) or cermets (NiCr-CrC) can be processed into layers using thermal coating processes. The basis for this is either a powder mixture or a composite powder. However, mechanical mixtures generally provide the lowest layer qualities, since the bond is only formed in the coating process and the hard materials have to be relatively large due to the required flow properties. Compound powders are usually produced by agglomeration into so-called micropellets. Here, microfine starting powders become processable in a spray drying process, i.e. primarily processed free-flowing powders. In order to increase the strength of the agglomerate or to achieve certain agglomerate densities, these are usually sintered. Another possibility of composite powder production is to mix the components with subsequent sintering to form a block. The powder is obtained here by breaking and grinding the block. Furthermore, composite powders are made by coating, for example a hard material powder is chemically or physically coated by a metallic element, or so-called cladding - fine metal powders are glued to the hard material core in a spray drying process.

Kennzeichnend für die Herstellung üblicher Verbundpulver ist, daß eine Verbundbildung im Pulver in aller Regel einen Sinterprozeß erfordert, da die Pulver ansonsten in den Beschichtungsprozeßen in ihre Ausgangsbestandteile zerfallen können und der vorteilhafte Verbundeffekt in der Schicht verloren geht. Dies ist um so wichtiger, je stärker die Verarbeitungskräfte während der Beschichtung werden. Diese sind insbesondere bei den Hochgeschwindigkeits-Spritzverfahren, wo die Pulver in einem Überschall-Gasstrom verarbeitet werden, sehr hoch. Des weiteren ist zur Erfüllung der tribologischen Aufgabe eine optimale Anbindung zwischen Keramik- und metallischer Bindephase notwendig, die insbesondere durch eine chemische-metallische Verbindung erreicht wird.It is characteristic of the production of conventional composite powders that the formation of a composite in the powder generally requires a sintering process, since otherwise the powders can disintegrate into their starting components in the coating processes and the advantageous composite effect is lost in the layer. This is all the more important the stronger the processing forces become during the coating. These are very high, especially in the high-speed spraying process, where the powders are processed in a supersonic gas stream. Furthermore, an optimal connection between the ceramic and metallic binding phase is necessary to fulfill the tribological task, which is achieved in particular by a chemical-metallic connection.

Nachteilig an der erforderlichen Sinterung ist, daß einerseits die Wirtschaftlichkeit der Pulver verringert wird, zum anderen eine Sinterfähigkeit der Ausgangskomponenten erforderlich ist. Diese ist insbesondere bei der Kombination WC-Co vorhanden, ist aber bei der aus wirtschaftlichen und tribologischen Gesichtspunkten interessanten Kombination aus z.B. metallischem Binder und oxidkeramischen Hartstoffen nicht gegeben. Daher konnten solche Pulver zur thermischen Beschichtung von Kolbenringlauffiächen bislang nicht erfolgreich eingesetzt werden. Ein Ansatz zur thermischen Beschichtung von Metallteilen, wie beispielsweise Kolbenringen und Zylinderlaufbuchsen, wird in DE 197 00 835 AI beschrieben. Das in diesem Dokument verwendete Kompositpulver ist ein Gemisch aus Karbiden, Metallpulver und Festschmierstoffen, dass mittels eines Hochgeschwindigkeits-Flammspritz-Nerfahrens zu einer selbstschmierenden Kompositschicht verarbeitet wird. Zur Erzeugung des Kompositpulvers werden die Kompositpartikel aus CrC und ΝiCr mit den Festschmierstoffen vermischt.A disadvantage of the required sintering is that on the one hand the economy of the powder is reduced, and on the other hand a sinterability of the starting components is required. This is particularly the case with the WC-Co combination, but is not available with the combination of, for example, metallic binder and oxide-ceramic hard materials, which is interesting from an economic and tribological point of view. Therefore, such powders have so far not been successfully used for the thermal coating of piston ring running surfaces. An approach to the thermal coating of metal parts, such as piston rings and cylinder liners, is described in DE 197 00 835 AI. The composite powder used in this document is a mixture of carbides, metal powder and solid lubricants that is processed into a self-lubricating composite layer using a high-speed flame spraying process. To create the composite powder, the composite particles made of CrC and ΝiCr are mixed with the solid lubricants.

Nachteilig an dieser Art der Erzeugung des Kompositpulvers gemäß DE 197 00 835 AI ist, dass zum Erhalt der notwendigen Rieselfähigkeit, als Bedingung für die Verarbeitung im Hochgeschwindigkeits-Flammspritz-Verfahren, relativ grobkörnige Partikel gebildet werden müssen. Bei diesen gemischten, nicht sphärischen Kompositpulvern muß die Korngröße der Festschmierstof artikel >20μm betragen, damit das Kompositpulver die zum Verspritzen im Hochgeschwindigkeits-Flammspritz-Verfahren erforderliche Rieselfähigkeit besitzt. Diese groben Partikel bedingen in der Beschichtung eine konzentrierte Anhäufung von Festschmierstoffphasen was sich wiederum negativ auf den Verschleiß auswirkt, da die groben und damit auch relativ großen Festschmierstoffbereiche herausbrechen können und durch Ihre Größe als Schmierstoff nur punktuell zur Verfügung stehen.A disadvantage of this type of production of the composite powder according to DE 197 00 835 AI is that in order to obtain the necessary flowability, as a condition for processing in the high-speed flame spraying process, relatively coarse particles have to be formed. With these mixed, non-spherical composite powders, the grain size of the solid lubricant article must be> 20 μm so that the composite powder has the flowability required for spraying in the high-speed flame spraying process. These coarse particles cause a concentrated accumulation of solid lubricant phases in the coating, which in turn has a negative effect on wear, since the coarse and thus also relatively large solid lubricant areas can break out and are only available selectively due to their size as a lubricant.

Daher ist es Aufgabe der vorliegenden Erfindung die beschichtungsseitigen Werkstoffkombinationen pulvertechnisch dahingehend zu erweitern, daß für den Kolbenring tribologisch optimale Oberflächen entstehen.It is therefore an object of the present invention to expand the material combinations on the coating side in terms of powder technology in such a way that tribologically optimal surfaces are created for the piston ring.

Es soll daher eine thermisch auftragbare Beschichtungszusammensetzung für Laufflächen von Kolbenringen etc. bereit gestellt werden, die aus mechanisch legierten Pulvern hergestellt werden können.It is therefore intended to provide a thermally applicable coating composition for running surfaces of piston rings etc., which can be produced from mechanically alloyed powders.

Erfϊndungsgemäß wird diese Aufgabe durch die Beschichtung gemäß Patentanspruch 1 sowie durch den Kolbenring gemäß Patentanspruch 11 gelöst.According to the invention, this object is achieved by the coating according to claim 1 and by the piston ring according to claim 11.

In den Unteransprüchen sind vorteilhafte Ausführungsformen der Erfindung enthalten.Advantageous embodiments of the invention are contained in the subclaims.

Erfindungsgemäß werden daher die Ausgangspulver mechanisch legiert, insbesondere in Attritoren, Hammer- oder Kugelmühlen. Bei allen diesen erfindungsgemäßen Verfahren werden Ausgangspulver klein gebrochen und dabei gleichzeitig ineinander verknetet, so daß auch ohne Sinterung ein Verbundpulver entsteht. Dadurch können auch nicht sintergeeignete Werkstoffkombinationen wie Metalle und Oxide zu Verbundpulvern verarbeitet werden. Diese Technologie wird beispielsweise großtechnisch zur Herstellung von so genannten ODS-Legierungen für Hochtemperaturanwendungen verwendet, wo der metallischen Matrix ca. 2 Gew.-% auf Nanodimension zerkleinerte Oxide zulegiert werden.According to the invention, the starting powders are therefore alloyed mechanically, in particular in attritors, hammer mills or ball mills. In all of these methods according to the invention, starting powders are broken down and kneaded into one another at the same time, so that a composite powder is formed even without sintering. As a result, combinations of materials such as metals and oxides that are not suitable for sintering can be processed to composite powders. This technology is used, for example, on an industrial scale to produce so-called ODS alloys for high-temperature applications, where about 2% by weight of oxides comminuted to the nanodimension are added to the metallic matrix.

Die Erfindung betrifft daher die Herstellung mechanisch legierter Pulver und Verwendung dieser Pulver mittels thermischer Beschichtungsverfahren zum Zwecke der Beschichtung der Laufflächen- und Flanken von Kolbenringen sowie daraus hergestellte Kolbenring- Beschichtungen. Die erfindungsgemäß eingesetzten Ausgangspulver besitzen eine geeignete Korngröße. Für das thermische Spritzen werden vorzugsweise Korngrößen von 5-80μm, besonders bevorzugt 5- 60μm, verwendet. Erfindungsgemäß besteht das Ausgaηgspulver aus einer metallischen Matrix und mindestens einer keramischen Phase zur Erhöhung der Verschleißbeständigkeit der metallischen Matrix. Die keramischen Phasen im Ausgangspulver bzw. in der fertigen Beschichtung besitzen Durchmesser von <10μm. Vorzugsweise besitzen sie Größenbereiche von wenigen Nanometern bis einigen Mikrometern. Die metallische Matrix des Ausgangspulvers und der Beschichtung umfassen insbesondere Legierungen auf Basis von Eisen, Nickel, Chrom, Kobalt, Molybdän.The invention therefore relates to the production of mechanically alloyed powders and the use of these powders by means of thermal coating processes for the purpose of coating the tread and flanks of piston rings and piston ring coatings produced therefrom. The starting powders used according to the invention have a suitable particle size. For thermal spraying, grain sizes of 5-80 μm, particularly preferably 5-60 μm, are preferably used. According to the invention, the starting powder consists of a metallic matrix and at least one ceramic phase to increase the wear resistance of the metallic matrix. The ceramic phases in the starting powder or in the finished coating have diameters of <10 μm. They preferably have size ranges from a few nanometers to a few micrometers. The metallic matrix of the starting powder and the coating comprise in particular alloys based on iron, nickel, chromium, cobalt, molybdenum.

Das Ausgangspulver kann aus einer metallischen Matrix und mindestens einer Festschmierstof hase zur Verbesserung der Schmiereigenschaften der Matrix bestehen. Die Festschmierstoffphase in dem Ausgangspulver besitzt Korngrößen < 20μm, bevorzugt < lOμm. Als Festschmierstoffpartikel können beispielsweise solche aus Graphit, hexagonalem Bornitrid oder Polytetrafluorethylen verwendet werdenThe starting powder can consist of a metallic matrix and at least one solid lubricant to improve the lubricating properties of the matrix. The solid lubricant phase in the starting powder has grain sizes <20 μm, preferably <10 μm. As solid lubricant particles, for example, those made of graphite, hexagonal boron nitride or polytetrafluoroethylene can be used

Ein weiterer Vorteil des erfindungsgemäßen Werkstoffes ergibt sich gegenüber der DE 197 00 835 AI dadurch, dass die Dispersoide und Festschmierstoffe zu einem Kompositpulver vermählen, d. h. mechanisch zulegiert, werden. Hierdurch können sehr feine Kompositpartikel erzeugt werden, die sich wiederum als feinst verteilte Festschmierstoffphasen in der Schicht wiederfinden. Diese feinst verteilten Festschmierstoffphasen ermöglichen nun eine optimale und gleichmäßige Verteilung der Schmiermittel, wodurch der Verschleiß der Schicht reduziert wird.Another advantage of the material according to the invention compared to DE 197 00 835 AI is that the dispersoids and solid lubricants grind to a composite powder, i. H. mechanically alloyed. In this way, very fine composite particles can be generated, which in turn are found in the layer as finely distributed solid lubricant phases. These finely distributed solid lubricant phases now enable optimal and even distribution of the lubricants, which reduces wear on the layer.

Weiterhin ist es möglich, dem erfindungsgemäßen Werkstoff auch Hartstoffpartikel beispielsweise aus der Gruppe Wolframkarbid, Chromkarbid, Aluminiumoxid, Silicium- karbid, Borkarbid, Titancarbid und/oder Diamant einzuarbeiten.It is also possible to incorporate hard material particles, for example from the group of tungsten carbide, chromium carbide, aluminum oxide, silicon carbide, boron carbide, titanium carbide and / or diamond, into the material according to the invention.

Das mechanische Legieren erlaubt unter prinzipieller Wahrung wirtschaftlicher Vorteile zwei wesentliche Vorteile gegenüber allen anderen Pulverherstellmethoden. Zum einen können prozeßtechnisch relativ einfach Verbundpulver wie Metall+Oxidkeramik und Metall+Diamant zur nachfolgenden beschichtungstechnischen Verarbeitung mittels thermischer Verfahren hergestellt werden. Dabei können die Gehalte an Hartstoffen in der Metallmatrix weit über 50 Vol.-% betragen, wodurch sich die Eigenschaften der Hartstoffphasen deutlich besser nutzen lassen als bei den niedrigen Gehalten, die heute beispielsweise bei galvanischen Chrom-Dispersionsschichten erreicht, werden. Als weiterer Vorteil können praktisch beliebig feine und homogen verteilte Hartstoffphasen in der beliebig zusammengesetzten Metallmatrix erzeugt werden. Hierdurch kann sowohl die Matrix gezielt auf Abrieb- und Brandspurfestigkeit optimiert werden als auch ein bestimmter Anteil von größeren Hartphasen rein tribologische Aufgaben erfüllen.Mechanical alloying allows two major advantages over all other powder production methods while maintaining economic advantages. On the one hand, composite powders such as metal + oxide ceramic and Metal + diamond can be produced for subsequent coating processing using thermal processes. The hard material contents in the metal matrix can be well over 50% by volume, which means that the properties of the hard material phases can be used much better than the low contents achieved today, for example, with galvanic chromium dispersion layers. As a further advantage, virtually arbitrarily fine and homogeneously distributed hard material phases can be generated in the metal matrix of any composition. In this way, the matrix can be specifically optimized for resistance to abrasion and burn marks, and a certain proportion of larger hard phases can perform purely tribological tasks.

Bei der Herstellung mechanisch legierter Pulver werden die Ausgangswerkstoffe in die Mühle eingefüllt und der Mahlprozeß gestartet. Die Pulver werden durch Stoßprozesse, die entweder durch die im Mischer enthaltenen Kugeln oder durch Kontakt mit den Kammerwänden erzeugt werden, je nach Verformbarkeit gebrochen bzw. verformt. Keramiken beispielsweise, die über keine Verformbarkeit verfügen, werden kontinuierlich klein gebrochen. Versuche haben gezeigt, daß diese bis auf Nanodimension herunter gebrochen werden können. Es hat sich ebenfalls gezeigt, daß die metallische Matrix bei Unterschreitung der darin enthaltenen Keramikphasen unterhalb der Ein-Mikron-Grenze deutliche Festigkeitssteigerungen erfährt. Metalle mit Verformungsvermögen werden dagegen weitestgehend nur verformt, teilweise durch versprödende Kaltverfestigung aber auch gebrochen. Im Laufe des Mahlprozesses werden dann die gebrochenen Hartstoffphasen in die Metallmatrix einlegiert und durch die fortdauernde Mahlbewegung zu verarbeitungsfähigen Pulverfraktionen verknetet. Es kommt dabei auch ohne Sinterung eine ausgezeichnete Anbindung zwischen beispielsweise Oxidkeramiken und Metallen zustande. Begründet wird dies damit, daß durch den Brechprozeß an der Keramik kontinuierlich frische, energiereiche Oberflächen erzeugt werden, die eine hohe mikroskopische Affinität besitzen. Durch die hohen mechanischen Impulse während des Mahlens werden die metallischen und keramischen Oberflächen so stark miteinander verpreßt, daß es vermutlich auf atomarer Ebene zu Grenzflächenreaktionen kommt. Eine anschließende Sinterung der Pulver kann in einzelnen Fällen eine weitere Steigerung der Keramik-Metall Kohäsion erzeugen.In the production of mechanically alloyed powders, the starting materials are filled into the mill and the grinding process is started. The powders are broken or deformed by impact processes, which are generated either by the balls contained in the mixer or by contact with the chamber walls, depending on the deformability. For example, ceramics that have no deformability are continuously broken down. Experiments have shown that these can be broken down to the nanodimension. It has also been shown that the metallic matrix experiences significant increases in strength when the ceramic phases contained in it fall below the one-micron limit. In contrast, metals with deformability are largely only deformed, but sometimes also broken by embrittling work hardening. In the course of the grinding process, the broken hard material phases are alloyed into the metal matrix and kneaded into processable powder fractions by the continuous grinding movement. There is an excellent bond between, for example, oxide ceramics and metals, even without sintering. This is justified by the fact that the ceramic breaking process continuously produces fresh, high-energy surfaces which have a high microscopic affinity. Due to the high mechanical impulses during milling, the metallic and ceramic surfaces are pressed together so strongly that interface reactions probably occur at the atomic level. Subsequent sintering of the powders can, in individual cases, further increase the ceramic-metal cohesion.

Durch Zuführung der verschiedenen Ausgangswerkstoffe zu unterschiedlichen Zeitpunkten können die Hartstoffgrößen im Pulver gezielt eingestellt werden. Es können darüber hinaus nicht nur eine Hartstoffphase und eine Metallmatrix als Ausgangswerkstoffe dienen, sondern praktisch beliebig viele. Zudem kann dem Pulver ein für die Anwendung nützlicher Anteil an Festschmierstoffen zusätzlich zugeführt werden. Die Pulver werden anschließend durch thermische Beschichtungsverfahren aufgetragen, wobei insbesondere gut das Thermische Spritzen, das Laserbeschichten sowie das Auftragschweißen und -löten eingesetzt werden können.By feeding the different starting materials at different times, the hard material sizes in the powder can be set in a targeted manner. In addition, not only a hard material phase and a metal matrix can serve as starting materials, but practically any number. In addition, a proportion of solid lubricants useful for the application can also be added to the powder. The powders are then applied by thermal coating processes, in particular thermal spraying, laser coating and hardfacing and soldering can be used.

In Versuchen wurde dabei vorrangig das Hochgeschwindigkeits-Flammspritzen (HVOF) aus der Familie des Thermischen Spritzens angewandt.In experiments, high-speed flame spraying (HVOF) from the thermal spraying family was primarily used.

Die Erfindung soll nun anhand der folgenden Beispiele sowie der Figuren (Bild 1, Bild 2) näher erläutert werden.The invention will now be explained in more detail with reference to the following examples and the figures (image 1, image 2).

Beispiel 1 :Example 1 :

In Beispiel 1 wurde konventionelles Spritzpulver von Aluminiumoxid mit einem konventionellem Spritzpulver aus NiCr im Volumenverhältnis 1:1 gemahlen. Dabei entstand nach dem Mahlprozeß ein Pulver feinst verteilter Aluminiumoxidphasen (grau) in der Matrix (Bild 1: mechanisch legiertes Pulver NiCr-34Al2O3). Nach Verarbeitung mittels HVOF entsteht eine sehr gut haftende, dichte Beschichtung, die zum Pulver eine gleiche MikroStruktur aufweist (Bild 2: HVOF-gespritzte Schicht zeigt identische MikroStrukturen).In Example 1, conventional wettable powder of aluminum oxide was ground with a conventional NiCr wettable powder in a volume ratio of 1: 1. After the grinding process, a powder of finely distributed aluminum oxide phases (gray) was created in the matrix (Figure 1: mechanically alloyed powder NiCr-34Al 2 O 3 ). After processing with HVOF, a very well adhering, dense coating is created, which has the same microstructure as the powder (Figure 2: HVOF-sprayed layer shows identical microstructures).

Beispiel 2:Example 2:

In Beispiel 2 wurde dem Pulver aus Beispiel 1 bis zu 20 Vol.-% eines pulverförmigen Festschmierstoffes zulegiert, der nach Verarbeitung mittels HVOF in der Schicht nachweislich vorhanden ist und das Reibverhalten der Schicht auf dem Kolbenring eindeutig verbessert. In Example 2, up to 20 vol.% Of a powdered solid lubricant was added to the powder from Example 1, which is demonstrably present in the layer after processing by means of HVOF and clearly improves the friction behavior of the layer on the piston ring.

Beispiel 3:Example 3:

In Beispiel 3 wurden der Matrix aus Beispiel 1 weitere metallische Elemente wie z.B. Mo zulegiert, um die tribologischen Eigenschaften der Kolbenringbeschichtung zu verbessern. Das Mo-Pulver wird im Mahlprozeß wegen seiner hohen Zähigkeit nur geringfügig feingemahlen, liegt aber im Pulver und in der Beschichtung als homogen verteilte, hervorragend eingebettete Phase vor. Das Brandspurverhalten der Kolbemingbeschichtung konnte auf diese Weise nachweisbar verbessert werden.In Example 3, the matrix from Example 1 was further metallic elements such as Mo alloyed to improve the tribological properties of the piston ring coating. The Mo powder is only slightly finely ground in the grinding process because of its high toughness, but is present in the powder and in the coating as a homogeneously distributed, excellently embedded phase. The fire trace behavior of the Kolbeming coating was demonstrably improved in this way.

Beispiel 4:Example 4:

In Beispiel 4 wurde dem Pulver aus Beispiel 1 50 Vol.-% zweier verschiedener keramischer Phasen (Aluminiumoxid, Zirkonoxid) zugemischt. Dabei wurden die Keramiken zu verschiedenen Zeitpunkten dem Mahlprozeß zugegeben, wodurch die verschiedenen keramischen Phasen in der HVOF Schicht unterschiedliche Fraktionen haben. Durch diese Vorgehensweise läßt sich durch die eine Keramik die Matrixhärte gezielt steuern, ohne daß die tribologisch erforderliche Hartphasengröße der anderen Keramik nachteilig beeinflußt wird. Dadurch kann die Abriebfestigkeit der Kolbemingbeschichtung eindeutig verbessert werden.In Example 4, 50% by volume of two different ceramic phases (aluminum oxide, zirconium oxide) were added to the powder from Example 1. The ceramics were added to the grinding process at different times, which means that the different ceramic phases in the HVOF layer have different fractions. This procedure allows one ceramic to control the matrix hardness in a targeted manner without adversely affecting the tribologically required hard phase size of the other ceramic. This clearly improves the abrasion resistance of the Kolbeming coating.

Beispiel 5:Example 5:

In Beispiel 5 wurde einem kommerziellen NiCr Spritzpulver feinster Diamantstaub zugemischt und einlegiert. Nach Verarbeitung mittels HVOF konnte eine Erhöhung der Verschleißbeständigkeit gegenüber der unlegierten Matrix festgestellt werden, was sich vorteilhaft auf die tribologischen Eigenschaften der Kolbemingbeschichtung auswirkt. In Example 5 the finest diamond dust was admixed and alloyed into a commercial NiCr wettable powder. After processing with HVOF, an increase in wear resistance compared to the unalloyed matrix was found, which has an advantageous effect on the tribological properties of the Kolbeming coating.

Claims

Titel: Thermisch aufgetragene Beschichtung für Kolbenringe aus mechanisch legierten PulvernAnsprüche Title: Thermally applied coating for piston rings made of mechanically alloyed powder 1. Verschleißfeste Beschichtung für Laufflächen und Flanken von Kolbenringen aus mechanisch legierten Pulvern, erhältlich durch mechanisches Legieren von1. Wear-resistant coating for running surfaces and flanks of piston rings made of mechanically alloyed powders, obtainable by mechanically alloying - Pulvern bestehend aus Nickel oder Eisen und einem oder mehreren der Nickel- oder Eisenlegierungselemente Kohlenstoff, Silizium, Chrom, Molybdän, Cobalt sowie Eisen oder Nickel, als metallische Matrix, in einer Menge von 70 bis 5 Vol.-%, bezogen auf das Gesamtgemisch, wobei der Anteil der Legierungselemente zusammen nicht mehr als 70 Gew.-% der Gesamtlegierung der Matrix beträgt,- Powders consisting of nickel or iron and one or more of the nickel or iron alloy elements carbon, silicon, chromium, molybdenum, cobalt and iron or nickel, as a metallic matrix, in an amount of 70 to 5 vol .-%, based on the total mixture , the proportion of the alloy elements together not exceeding 70% by weight of the total alloy of the matrix, - einem oder mehreren der Dispersoide Al2O3, Cr203, TiO2, Zr02, Fe3O , TiC, SiC, CrC, WC, BC oder Diamant, wobei die Teilchengröße des oder der Dispersoide(s) bis etwa 10 μm beträgt und der Anteil der Dispersoiden am Gesamtgemisch zwischen 30 und 95 Vol.-% beträgt, und Auftragen des mechanisch legierten Pulvers mittels thermischem Spritzen.- One or more of the dispersoids Al 2 O 3 , Cr 2 0 3 , TiO 2 , Zr0 2 , Fe 3 O, TiC, SiC, CrC, WC, BC or diamond, the particle size of the dispersoid (s) being approximately 10 μm and the proportion of dispersoids in the total mixture is between 30 and 95 vol.%, And application of the mechanically alloyed powder by means of thermal spraying. 2. Verschleißfeste Beschichtung gemäß Anspruch 1, mechanisch legiert mit Anteilen aus pulverförmigen Festschmierstoffen aus der Gruppe aus Graphit, hexagonalem Bornitrid,2. Wear-resistant coating according to claim 1, mechanically alloyed with portions of powdered solid lubricants from the group consisting of graphite, hexagonal boron nitride, Polytetrafluorethylen, wobei der Anteil der pulverförmigen Festschmierstoffe bis zu 30 Vol.-% des Gesamtgemisches beträgt.Polytetrafluoroethylene, the proportion of powdered solid lubricants being up to 30% by volume of the total mixture. 3. Verschleißfeste Beschichtung nach einem der Ansprüche 1 und/oder 2, mechanisch legiert mit Anteilen aus einem oder mehreren Additiven aus der Gruppe der Elemente Ti,3. Wear-resistant coating according to one of claims 1 and / or 2, mechanically alloyed with fractions of one or more additives from the group of the elements Ti, Zr, Hf, AI, Si, P, B in einer Menge von bis zu 2 Gew.-%, bezogen auf die Gesamtlegierung der metallischen Matrix.Zr, Hf, Al, Si, P, B in an amount of up to 2% by weight, based on the total alloy of the metallic matrix. 4. Verschleißfeste Beschichtung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die keramische Phase 70 bis 90 Vol.-% beträgt.4. Wear-resistant coating according to one of claims 1 to 3, characterized in that the ceramic phase is 70 to 90 vol .-%. 5. Verschleißfeste Beschichtung gemäß einem der vorhergehenden Anspruch 1 bis 4, dadurch gekennzeichnet, daß die metallische Matrix als Nickel mit bis zu 50 Gew.-% Chrom vorliegt. 5. Wear-resistant coating according to one of the preceding claims 1 to 4, characterized in that the metallic matrix is present as nickel with up to 50 wt .-% chromium. 6. Verschleißfeste Beschichtung gemäß einem der vorhergehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die metallische Matrix aus Nickel mit bis zu 30 Gew.-% Chrom und bis zu 30 Gew.-% Molybdän besteht.6. Wear-resistant coating according to one of the preceding claims 1 to 4, characterized in that the metallic matrix consists of nickel with up to 30 wt .-% chromium and up to 30 wt .-% molybdenum. 7. Verschleißfeste Beschichtung gemäß einem der vorhergehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die metallische Matrix als Eisen mit bis zu 50 Gew.-% Chrom vorliegt.7. Wear-resistant coating according to one of the preceding claims 1 to 4, characterized in that the metallic matrix is present as iron with up to 50 wt .-% chromium. 8. Verschleißfeste Beschichtung gemäß einem der vorhergehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die metallische Matrix aus Eisen mit bis zu 30 Gew.-% Chrom und mit bis zu 30 Gew.-% Molybdän besteht.8. Wear-resistant coating according to one of the preceding claims 1 to 4, characterized in that the metallic matrix consists of iron with up to 30 wt .-% chromium and with up to 30 wt .-% molybdenum. 9. Verschleißfeste Beschichtung gemäß einem der vorhergehenden Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die keramische Phase aus Al2O3 besteht.9. Wear-resistant coating according to one of the preceding claims 1 to 8, characterized in that the ceramic phase consists of Al 2 O 3 . 10. Verschleißfeste Beschichtung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das mechanische Legieren in einer Hammermühle, einer Kugelmühle oder in einem Attritor durchgeführt wird.10. Wear-resistant coating according to one of the preceding claims, characterized in that the mechanical alloying is carried out in a hammer mill, a ball mill or in an attritor. 11. Kolbenring für Verbrennungsmaschinen, dadurch gekennzeichnet, daß der Kolbenring auf den Flankenflächen und/oder Lauffläche eine Beschichtung gemäß einem der vorhergehenden Ansprüche 1 bis 10 aufweist.11. Piston ring for internal combustion engines, characterized in that the piston ring has a coating on the flank surfaces and / or tread according to one of the preceding claims 1 to 10. 12. Kolbenring gemäß Anspruch 11, dadurch gekennzeichnet, daß die Dicke der Beschichtung 0,01 bis 1,0 mm beträgt.12. Piston ring according to claim 11, characterized in that the thickness of the coating is 0.01 to 1.0 mm. 13. Kolbenring gemäß Anspruch 11 und 12, dadurch gekennzeichnet, daß die Beschichtung mittels thermischem Spritzen, insbesondere mittels Hochgeschwindigkeits- Flammspritzen (HVOF) aufgebracht worden ist. 13. Piston ring according to claim 11 and 12, characterized in that the coating has been applied by means of thermal spraying, in particular by means of high-speed flame spraying (HVOF).
EP01976101A 2000-09-21 2001-08-17 Thermally applied coating for piston rings, consisting of mechanically alloyed powders Expired - Lifetime EP1322794B1 (en)

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PCT/EP2001/009514 WO2002024970A2 (en) 2000-09-21 2001-08-17 Thermally applied coating for piston rings, consisting of mechanically alloyed powders

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JP2004510050A (en) 2004-04-02
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