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EP1322794A2 - Revetement applique par voie thermique, destine a des segments de piston et constitue de poudres alliees mecaniquement - Google Patents

Revetement applique par voie thermique, destine a des segments de piston et constitue de poudres alliees mecaniquement

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)
English (en)
Other versions
EP1322794B1 (fr
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
Family has litigation
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Application filed by Federal Mogul Burscheid GmbH filed Critical Federal Mogul Burscheid GmbH
Publication of EP1322794A2 publication Critical patent/EP1322794A2/fr
Application granted granted Critical
Publication of EP1322794B1 publication Critical patent/EP1322794B1/fr
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.

Landscapes

  • 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)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un revêtement résistant à l'usure, destiné aux surfaces de frottement et flancs de segments de piston dans des moteurs à combustion interne. Ce revêtement est obtenu par alliage mécanique de poudres qui forment une matrice métallique avec des dispersoïdes de substances dures et de lubrifiants. Il est appliqué sur les pièces par voie thermique, notamment par projection à la flamme à haute vitesse (HVOF). Les pièces revêtues sont les surfaces de frottement et les parties de flancs de segments de piston dans des moteurs à combustion interne.
EP01976101A 2000-09-21 2001-08-17 Revetement applique par voie thermique, destine a des segments de piston et constitue de poudres alliees mecaniquement Expired - Lifetime EP1322794B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10046956A DE10046956C2 (de) 2000-09-21 2000-09-21 Thermisch aufgetragene Beschichtung für Kolbenringe aus mechanisch legierten Pulvern
DE10046956 2000-09-21
PCT/EP2001/009514 WO2002024970A2 (fr) 2000-09-21 2001-08-17 Revetement applique par voie thermique, destine a des segments de piston et constitue de poudres alliees mecaniquement

Publications (2)

Publication Number Publication Date
EP1322794A2 true EP1322794A2 (fr) 2003-07-02
EP1322794B1 EP1322794B1 (fr) 2008-05-28

Family

ID=7657203

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01976101A Expired - Lifetime EP1322794B1 (fr) 2000-09-21 2001-08-17 Revetement applique par voie thermique, destine a des segments de piston et constitue de poudres alliees mecaniquement

Country Status (6)

Country Link
US (1) US6887585B2 (fr)
EP (1) EP1322794B1 (fr)
JP (1) JP2004510050A (fr)
DE (1) DE10046956C2 (fr)
PT (1) PT1322794E (fr)
WO (1) WO2002024970A2 (fr)

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US6887585B2 (en) 2005-05-03
DE10046956A1 (de) 2002-04-25
PT1322794E (pt) 2008-07-30
US20030180565A1 (en) 2003-09-25
JP2004510050A (ja) 2004-04-02

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