EP1341946B1 - Couche d'usure pour segments de piston renfermant du carbure de tungstene et du carbure de chrome - Google Patents

Couche d'usure pour segments de piston renfermant du carbure de tungstene et du carbure de chrome Download PDF

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Publication number
EP1341946B1
EP1341946B1 EP01270182A EP01270182A EP1341946B1 EP 1341946 B1 EP1341946 B1 EP 1341946B1 EP 01270182 A EP01270182 A EP 01270182A EP 01270182 A EP01270182 A EP 01270182A EP 1341946 B1 EP1341946 B1 EP 1341946B1
Authority
EP
European Patent Office
Prior art keywords
chromium
carbides
piston ring
carbide
powder
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.)
Expired - Lifetime
Application number
EP01270182A
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German (de)
English (en)
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EP1341946A1 (fr
Inventor
Christian Herbst-Dederichs
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Federal Mogul Burscheid GmbH
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Federal Mogul Burscheid GmbH
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Publication date
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Publication of EP1341946A1 publication Critical patent/EP1341946A1/fr
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—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
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • Y10T428/12181—Composite powder [e.g., coated, etc.]
    • 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
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]
    • 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
    • Y10T428/1284—W-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 piston ring for internal combustion engines at least one peripheral surface of the piston ring by means of thermal spraying applied wear protection layer, essentially consisting of chrome carbides, Tungsten carbide, chrome and nickel.
  • the running surfaces of piston rings in internal combustion engines are subject to wear during use.
  • a protective layer is applied to the running surfaces of the piston rings to minimize wear.
  • the coating material which is in the form of a powder, is melted by means of an oxygen / fuel spray gun and sprayed onto the piston ring.
  • EP 0 960 954 A2 discloses a corresponding powder for producing these wear protection layers. This powder contains nickel, chromium and carbon, whereby the chromium can be present as chromium carbide and as a nickel-chromium alloy.
  • the carbides are present in an already decomposed form, so that the matrix becomes brittle and the carbides lose hardness due to conversion from Cr3C2 to Cr7C3 or even to Cr23C6.
  • DE 197 20 627 A1 mixes 20 to 80% by volume of molybdenum with the wettable powder. Molybdenum has a relatively high toughness and can therefore stop crack growth.
  • the patent application discloses preferred coatings of sintered chromium carbide and nickel chromium powders with up to 100% by weight of molybdenum.
  • phase of molybdenum are formed in the resulting layer, which are approximately the size of the starting powder and generally have a diameter of 5 to 50 ⁇ m.
  • the relatively low abrasion resistance of the molybdenum has a negative effect, the molybdenum phases are preferably worn out and consequently the wear resistance of the protective layer decreases.
  • tungsten carbides are also embedded in the matrix of the wear protection layer.
  • European patent EP 0 512 805 B1 describes the formation of a surface protection with chromium and tungsten carbides, the embedded tungsten-chromium carbides having a particle size in the range from 25 to 100 ⁇ m.
  • Tungsten carbides are harder than chrome carbides and have a very high resistance to pressure and wear.
  • the extraordinarily hard tungsten carbides also show a clear disadvantage when processing the surface produced. The surface can no longer be processed with conventional grinding wheels, processing is only possible with very high quality and at the same time expensive grinding wheels.
  • EP -A- 0657237 discloses a thermal wettable powder consisting of Tungsten carbide particles which are connected by metallic cobalt are.
  • a second type of grains consisting of chrome carbide particles connected to each other via a Ni-Cr alloy.
  • the protective layer is for High pressure valves, petrochemical lines, seats in pumps etc. are used. A Application for piston rings is not mentioned.
  • a coating for piston rings can be found in US-A-3606359 different microstructure than in the present application. There will be two various powders sprayed from previously sintered particles; an indication of the The size of the particles for the carbides is not mentioned.
  • the invention is based on the object belonging to the prior art To overcome disadvantages and to produce a piston ring for internal combustion engines, which has a wear protection layer on the tread that is almost crack-free and a has high wear resistance.
  • the wear protection layer according to the invention for the running surface of the piston ring is formed from a powder mixture in which the first powder as agglomerated and sintered powder consists at least of the alloy components chromium carbide, chromium and nickel, which does not have any subsequent embrittling heat treatment such as, for. B.
  • the carbides in the powder having an average diameter which is less than 3 microns and a second powder, which is also present as an agglomerated and sintered powder and contains tungsten carbide as an essential feature and by thermal spraying on at least a circumferential surface of the piston rings is applied, so that two distinguishable layer regions are produced in the wear protection layer, a first region which is primarily rich in chromium carbide and a second region which is mainly rich in tungsten carbide.
  • the use of a powder with a carbide size of less than 3 ⁇ m is a significant difference to the conventionally used powders, whose average carbide size is over 5 ⁇ m, but mostly even over 10 ⁇ m.
  • the carbide breakout is reduced, the risk of cracks is minimized and at the same time the residual stresses in the carbide are reduced, which in turn reduces the tendency to carbide breakdown.
  • Another essential difference is the use of primary carbides in the starting powder, which are mainly in the form of blocky Cr3C2 and Cr7C3 carbides.
  • the powders obtained via conventional melt atomization on the other hand, mostly have dendritic carbides and mostly dissolved carbides such as Cr23C6, which are much softer.
  • two distinguishable layer areas form as the basis in the wear protection layer.
  • the layer structure is disordered.
  • the first layer area forms, for example, a matrix of nickel, chromium and molybdenum, in which chromium carbides and phases rich in molybdenum are embedded homogeneously and finely distributed.
  • the molybdenum phases are only of a size of not larger than 5 ⁇ m, so that there are no wear-increasing phases in the matrix.
  • tungsten and chromium carbides are clearly embedded in the nickel matrix.
  • the average tungsten carbide has a diameter that is not larger than 1.5 ⁇ m and the chrome carbide has a diameter that is smaller than 3 ⁇ m, which supports machining.
  • a ratio corresponding to this layer structure could, for example, consist of 2 parts of areas rich in tungsten carbide and 8 parts of areas rich in chromium carbide.
  • Tests in real internal combustion engines have shown that a wear protection layer on the piston rings designed according to this example showed complete freedom from cracks and a wear behavior comparable to that of electroplated layers.
  • a resultant advantage is that processing with complete absence of cracks is possible without problems with conventional grinding wheels, that is, finishing is not more expensive than with a conventional wear protection layer produced by means of today's plasma spraying techniques.
  • the cobalt components in the alloy serve in particular as binders in the areas rich in tungsten carbide.
  • the hard material phases chrome carbide and tungsten carbide are the carriers of hardness and determine, among other things, the wear properties, while the binder metal gives the wear protection layer the toughness.

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

Claims (14)

  1. Segment de piston pour moteurs à combustion interne, comprenant une couche de protection contre l'usure appliquée par pulvérisation thermique sur au moins une surface périphérique du segment de piston, ladite couche étant constituée de carbures de chrome, de carbure de tungstène, de chrome et de nickel, caractérisé en ce que la couche de protection contre l'usure est constituée d'un mélange de poudre, dans lequel la première poudre est constituée au moins à partir des composants d'alliage constitués par le carbure de chrome, le chrome et le nickel sous la forme d'une poudre agglomérée et frittée, qui n'a connu aucun traitement thermique fragilisant préjudiciable comme par exemple un enrichissement au plasma, le carbure dans la poudre présentant un diamètre moyen, qui est inférieur à 3 µm et une deuxième poudre, qui se présente également sous la forme d'une poudre agglomérée et frittée et qui contient du carbure de tungstène, de telle sorte que deux zones de couches différenciables sont produites dans la couche de protection contre l'usure, une première zone riche en carbure de chrome de manière prépondérante et une seconde zone riche en carbure de tungstène principalement étant ainsi constituées.
  2. Segment de piston selon la revendication 1, caractérisé en ce que la seconde poudre contient en plus du chrome, du carbone et du nickel, de telle sorte qu'il se crée lors de la pulvérisation des zones riches en carbure de tungstène, dans lesquelles le carbure de tungstène, le carbure de chrome et de nickel sont prépondérants.
  3. Segment de piston selon l'une des revendications 1 et 2, caractérisé en ce que les pourcentages de constituants d'alliage dans les zones riches en carbure de tungstène sont présents dans des quantités de 8 à 11% pour le carbone, de 6 à 8% pour le nickel, de 18 à 24% pour le chrome et le reste de tungstène.
  4. Segment de piston selon la revendication 1, caractérisé en ce que la seconde poudre contient en outre du nickel, de telle sorte que des zones riches en carbure de tungstène sont créées lors de la pulvérisation dans lesquelles le carbure de tungstène et le nickel sont prépondérants.
  5. Segment de piston selon l'une des revendications 1 à 4, caractérisé en ce que les constituants d'alliages sont présents dans des quantités de 4 à 6% pour le carbone, de 11 à 18% pour le nickel, et le reste de tungstène.
  6. Segment de piston selon la revendication 1, caractérisé en ce que la seconde poudre contient en outre du cobalt et du chrome de telle sorte que des zones riches en carbure de tungstène sont créées lors de la pulvérisation dans lesquelles du carbure de tungstène est prépondérant dans un alliage cobalt-chrome.
  7. Segment de piston selon l'une des revendications 1 à 6, caractérisé en ce que les composants d'alliages sont présents avec des quantités de 6 à 18% de cobalt, de 0,01 à 9% de chrome et le reste de tungstène.
  8. Segment de piston selon l'une des revendications 1 à 7, caractérisé en ce que: les zones riches en carbure de chrome contiennent entre 7 et 10% de carbone, 10 à 20% de nickel, 1 à 10% de molybdène et le reste de chrome.
  9. Segment de piston selon l'une des revendications 1 à 8, caractérisé en ce que la quantité de zones riches en carbure de tungstène dans le mélange est située entre 1 et 95% en volume.
  10. Segment de piston selon l'une des revendications 8 et 9, caractérisé en ce que les diamètres des phases riches en molybdène dans les zones riches en carbure de chrome ne sont pas supérieurs à 5 µm.
  11. Segment de piston selon l'une des revendications 8 à 10, caractérisé en ce que les carbures de tungstène en moyenne ne sont pas supérieures à 1,5 µm.
  12. Segment de piston selon l'une des revendications 1 à 11, caractérisé en ce que les carbures de tungstène sont prépondérants sous la forme de carbure WC.
  13. Segment de piston selon l'une des revendications 1 à 12, caractérisé en ce que les carbures de chrome sont prépondérants sous la forme de carbure Cr3C2.
  14. Segment de piston selon l'une des revendications 1 à 13, caractérisé en ce que l'on utilise la pulvérisation par flamme à haute vitesse (HVOF) en tant que procédé de pulvérisation thermique.
EP01270182A 2000-12-12 2001-11-17 Couche d'usure pour segments de piston renfermant du carbure de tungstene et du carbure de chrome Expired - Lifetime EP1341946B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10061750 2000-12-12
DE10061750A DE10061750B4 (de) 2000-12-12 2000-12-12 Wolframhaltige Verschleißschutzschicht für Kolbenringe
PCT/DE2001/004336 WO2002048422A1 (fr) 2000-12-12 2001-11-17 Couche d'usure pour segments de piston renfermant du carbure de tungstene et du carbure de chrome

Publications (2)

Publication Number Publication Date
EP1341946A1 EP1341946A1 (fr) 2003-09-10
EP1341946B1 true EP1341946B1 (fr) 2004-09-01

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EP01270182A Expired - Lifetime EP1341946B1 (fr) 2000-12-12 2001-11-17 Couche d'usure pour segments de piston renfermant du carbure de tungstene et du carbure de chrome

Country Status (7)

Country Link
US (1) US7001670B2 (fr)
EP (1) EP1341946B1 (fr)
JP (1) JP4394349B2 (fr)
AT (1) ATE275212T1 (fr)
BR (1) BR0116079B1 (fr)
DE (2) DE10061750B4 (fr)
WO (1) WO2002048422A1 (fr)

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DE102006049756A1 (de) * 2006-10-21 2008-04-24 Federal-Mogul Burscheid Gmbh Verschleißschutzschicht für Kolbenringe
US20100127462A1 (en) * 2007-01-09 2010-05-27 Michael Buchmann Piston ring with a multilayer assembly, and a method for the production thereof
US20090191416A1 (en) * 2008-01-25 2009-07-30 Kermetico Inc. Method for deposition of cemented carbide coating and related articles
DE102008014333B4 (de) 2008-03-14 2012-05-03 Federal-Mogul Burscheid Gmbh Verschleißfestes Bauteil
ATE544704T1 (de) * 2008-07-14 2012-02-15 Sulzer Metco Coatings Gmbh Tauchbadrolle und verfahren zum herstellen einer tauchbadrolle
DE102009016650B3 (de) * 2009-04-07 2010-07-29 Federal-Mogul Burscheid Gmbh Gleitelement mit einstellbaren Eigenschaften
US8906130B2 (en) 2010-04-19 2014-12-09 Praxair S.T. Technology, Inc. Coatings and powders, methods of making same, and uses thereof
DE102010038289A1 (de) * 2010-07-22 2012-01-26 Federal-Mogul Burscheid Gmbh Kolbenring mit thermischen gespritzter Beschichtung und Herstellungsverfahren davon
WO2013062045A1 (fr) 2011-10-25 2013-05-02 株式会社Ihi Segment de piston
BR102012016283A2 (pt) * 2012-06-29 2014-08-12 Mahle Metal Leve Sa Elemento deslizante e motor de combustão interna
US9890858B2 (en) 2012-06-29 2018-02-13 Mahle Metal Leve S/A Sliding element and internal combustion engine

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Also Published As

Publication number Publication date
US20040069141A1 (en) 2004-04-15
EP1341946A1 (fr) 2003-09-10
WO2002048422A1 (fr) 2002-06-20
JP4394349B2 (ja) 2010-01-06
DE10061750A1 (de) 2002-06-20
BR0116079B1 (pt) 2011-04-05
ATE275212T1 (de) 2004-09-15
DE10061750B4 (de) 2004-10-21
DE50103494D1 (de) 2004-10-07
BR0116079A (pt) 2003-12-16
US7001670B2 (en) 2006-02-21
JP2004514795A (ja) 2004-05-20

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