EP1341946B1 - Wear protection layer for piston rings, containing wolfram carbide and chromium carbide - Google Patents
Wear protection layer for piston rings, containing wolfram carbide and chromium carbide Download PDFInfo
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- 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
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- Prior art keywords
- chromium
- carbides
- piston ring
- carbide
- powder
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- 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
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- 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)
Abstract
Description
Die vorliegende Erfindung betrifft einen Kolbenring für Brennkraftmaschinen mit auf mindestens eine Umfangsfläche des Kolbenringes mittels thermischem Spritzen aufgetragenen Verschleißschutzschicht, im wesentlichen bestehend aus Chrom-Karbiden, Wolfram-Karbid, Chrom und Nickel.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.
Die Laufflächen von Kolbenringen in Verbrennungskraftmaschinen unterliegen
während ihres Einsatzes einem Verschleiß. Um den Verschleiß zu minimieren werden
die Laufflächen der Kolbenringe mit einer Schutzschicht beaufschlagt. Je nach
eingesetztem Fertigungsverfahren gehört es zum allgemeinen Stand der Technik, diese
Schichten mittels eines Hochgeschwindigkeits-Flammspritz-Verfahrens zu erzeugen.
Bei diesem Verfahren wird das Beschichtungsmaterial, das als Pulver vorliegt, mittels
einer Sauerstoff-/Brennstoff-Spritzpistole geschmolzen und auf den Kolbenring
aufgespritzt. Die EP 0 960 954 A2 offenbart ein entsprechendes Pulver zur Erzeugung
dieser Verschleißschutzschichten. Dieses Pulver enthält Nickel, Chrom und
Kohlenstoff, wobei das Chrom als Chrom-Karbid und als Nickel-Chrom-Legierung
vorliegen kann. Der Aufsatz: "The Application of Cermet Coating on Piston Ring by
HVOF" von H. Fukutome, aus dem Jahre 1995, des japanischen Kolbenringherstellers
Teikoku Piston Ring, beschreibt ebenfalls den Einsatz von Chrom-Karbiden und
Nickel-Chrom-Legierungen zur Erzeugung von Verschleißschichten mittels
Hochgeschwindigkeits-Flammspritzens. Die in beiden Schriften zum Einsatz
kommenden Legierungskomponenten bilden eine Nickel-Chrom-Matrix, in die je nach
Legierungsanteil Chrom-Karbide eingelagert sind. Nachteilig an diesen Schichten ist,
das sie aufgrund ihrer Härte und Sprödigkeit rissanfällig sind, wobei die
Rissanfälligkeit sogar der lebensdauerbestimmende Faktor für die Kolbenringe sein
kann. Diese Rissanfälligkeit resultiert aus den großen Karbiddurchmessern, was
spannungsbedingt zu Karbidausbrüchen und damit zum Ringverschleiß führt.
Insbesondere in den plasmabehandelten Pulvern liegen die Karbide in einer bereits
zersetzten Form vor, so dass die Matrix versprödet und die Karbide durch Umwandlung
vom Cr3C2 zu Cr7C3 oder sogar zu Cr23C6 an Härte verlieren. Um diesem Nachteil
entgegenzutreten werden in der DE 197 20 627 A1 dem Spritzpulver 20 bis 80 Vol-%
Molybdän zugemischt. Molybdän besitzt eine relativ hohe Zähigkeit und kann somit das
Risswachstum stoppen. Die Patentanmeldung offenbart bevorzugte Beschichtungen aus
gesinterten Chrom-Karbid- und Nickel-Chrom-Pulvern mit bis zu 100 Gew.-%
Molybdän. Durch das Einbringen des Molybdäns in das Pulver entstehen aber in der
daraus resultierenden Schicht Phasen aus Molybdän, die annähernd die Größe des
Ausgangspulvers besitzen und in der Regel einen Durchmesser von 5 bis 50 µm
besitzen. Negativ wirkt sich dabei die relativ niedrige Abriebbeständigkeit des
Molybdäns aus, die Molybdänphasen werden bevorzugt verschlissen und folglich
nimmt die Verschleißbeständigkeit der Schutzschicht ab.
Neben den Chrom-Karbiden werden auch Wolfram-Karbide in die Matrix der
Verschleißschutzschicht mit eingelagert. Die europäische Patentschrift EP 0 512 805 B1
beschreibt die Bildung eines Oberflächenschutzes mit Chrom- und Wolfram-Karbiden,
wobei die eingelagerten Wolfram-Chrom-Karbide eine Partikelgröße im Bereich von 25
- 100 µm aufweisen. Wolfram-Karbide sind härter als Chrom-Karbide und besitzen
eine sehr hohe Druck- und Verschleißbeständigkeit. Die außergewöhnlich harten
Wolfram-Karbide zeigen aber gleichzeitig einen deutlichen Nachteil bei der
Bearbeitung der erzeugten Oberfläche. Die Oberfläche kann mit herkömmlichen
Schleifscheiben nicht mehr bearbeitet werden, eine Bearbeitung ist lediglich mit sehr
hochwertigen und gleichzeitig teuren Schleifscheiben möglich.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. Depending on the manufacturing process used, it is part of the general state of the art to produce these layers using a high-speed flame spraying process. In this process, 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 article: "The Application of Cermet Coating on Piston Ring by HVOF" by H. Fukutome, from 1995, by the Japanese piston ring manufacturer Teikoku Piston Ring, also describes the use of chrome carbides and nickel-chrome alloys to create wear layers by means of high-speed flame spraying. The alloy components used in both documents form a nickel-chromium matrix in which, depending on the alloy content, chromium carbides are embedded. A disadvantage of these layers is that they are susceptible to cracking due to their hardness and brittleness, and the susceptibility to cracking can even be the life-determining factor for the piston rings. This susceptibility to cracking results from the large carbide diameters, which, due to the stress, leads to carbide breakouts and thus to ring wear. In the plasma-treated powders in particular, 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. In order to counter this disadvantage, 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. By introducing the molybdenum into the powder, however, phases 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 μm. 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.
In addition to the chrome carbides, 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 μm. Tungsten carbides are harder than chrome carbides and have a very high resistance to pressure and wear. The extraordinarily hard tungsten carbides, however, 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.
Die EP -A- 0657237 offenbart ein thermisches Spritzpulver bestehend aus Wolframkarbid- Partikeln welche durch metallisches Kobald miteinander verbunden sind. Darüber hinaus wird eine zweite Art Körner bestehend aus Chromkarbid-Partikeln über eine Ni-Cr- Legierung miteinander verbunden. Die Schutzschicht wird für Hochdruckventile, petrochemische Leitungen, Sitze in Pumpen etc. verwendet. Eine Anwendung für Kolbenringe ist nicht erwähnt. EP -A- 0657237 discloses a thermal wettable powder consisting of Tungsten carbide particles which are connected by metallic cobalt are. In addition, 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.
Aus der US -A- 3606359 ist eine Beschichtung für Kolbenringe zu entnehmen die eine andere Mikrostruktur als in der vorliegenden Anmeldung aufweist. Es werden zwei verschiedene Pulver aus vorher gesinterten Partikeln aufgespritzt; eine Angabe über die Größe der Partikel für die Karbide wird nicht erwähnt.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.
Der Erfindung liegt die Aufgabe zugrunde, die zum Stand der Technik gehörigen Nachteile zu überwinden, und einen Kolbenring für Brennkraftmaschinen zu erzeugen, der auf der Lauffläche eine Verschleißschutzschicht aufweist, die nahezu rissfrei ist und eine hohe Verschleißbeständigkeit besitzt.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.
Diese Aufgabe wird erfindungsgemäß durch den kennzeichnenden Teil des
Patentanspruchs 1 gelöst, vorteilhafte Weiterbildungen der Erfindung sind in den
Unteransprüchen dokumentiert.This object is achieved by the characterizing part of the
Solved
Die erfindungsgemäße Verschleißschutzschicht für die Lauffläche des Kolbenrings ist
aus einem Pulvergemisch gebildet, in dem das erste Pulver als agglomeriertes und
gesintertes Pulver mindestens aus den Legierungskomponenten Chrom-Karbid, Chrom
und Nickel besteht, das keine nachträgliche versprödende Wärmebehandlung wie z. B.
eine Plasmaveredlung erfahren hat, wobei die Karbide im Pulver einen mittleren
Durchmesser aufweisen, der weniger als 3 µm ist und einem zweiten
Pulver, das ebenfalls als agglomeriertes und gesintertes Pulver vorliegt und als
wesentliches Merkmal Wolfram-Karbid enthält und mittels thermischem Spritzens auf
mindestens eine Umfangsfläche der Kolbenringe aufgetragen ist, so dass in der
Verschleißschutzschicht zwei unterscheidbare Schichtbereiche erzeugt werden, wobei
sich ein erster vornehmlich chromkarbidreicher und ein zweiter hauptsächlich
wolframkarbidreicher Bereich ausbildet.
Der Einsatz eines Pulvers mit einer Karbidgröße von weniger als 3 µm ist ein
wesentlicher Unterschied zu den herkömmlich eingesetzten Pulvern, deren mittlere
Karbidgröße bei über 5 µm liegt, meistens jedoch sogar über 10 µm. Durch die
Verringerung der Karbidgröße wird der Karbidausbruch verringert, die Rissgefahr wird
minimiert und gleichzeitig werden die Eigenspannungen im Karbid reduziert was
wiederum die Karbidzerrüttungstendenz verkleinert. Ein weiterer wesentlicher
Unterschied ist der Einsatz von Primärkarbiden im Ausgangspulver, die vorwiegend als
blockige Cr3C2- und Cr7C3-Karbide vorliegen. Die über die herkömmliche
Schmelzverdüsung gewonnen Pulver weisen dagegen meist dendritische Karbide und
vorwiegend aufgelöste Karbide wie zum Beispiel Cr23C6 auf, die sehr viel weicher
sind.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. has undergone a plasma refinement, 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 µm is a significant difference to the conventionally used powders, whose average carbide size is over 5 µm, but mostly even over 10 µm. By reducing the carbide size, 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.
Erfindungsgemäß bilden sich zwei unterscheidbare Schichtbereiche als Basis in der
Verschleißschutzschicht aus. Dabei ist der Schichtaufbau ungeordnet. Den ersten
Schichtbereich bildet beispielsweise eine Matrix aus Nickel, Chrom und Molybdän aus,
in der homogen und fein verteilt Chrom-Karbide und molybdänreiche Phasen
eingelagert sind. Die Molybdänphasen liegen im Gegensatz zu den aus dem Stand der
Technik bekannten 5 bis 50 µm großen Molybdänphasen lediglich in einer Größe von
nicht größer als 5µm vor, so dass keine verschleißerhöhenden Phasen in der Matrix
vorliegen.
Im zweiten sichtlich unterscheidbaren Schichtbereich sind in die Nickel-Matrix
vernehmlich Wolfram- und Chrom-Karbide eingelagert. Dabei haben die Wolfram-Karbide
im Mittel einen Durchmesser, der nicht größer als 1,5 µm ist und die
Chrom-Karbide einen Durchmesser, der kleiner als 3 µm ist, wodurch
die spanende Bearbeitung unterstützt wird. Ein diesem Schichtaufbau entsprechendes
Verhältnis könnte beispielhaft aus 2-Teilen wolframkarbidreichen Bereichen und 8
Teilen chromkarbidreichen Bereichen bestehen. Versuche in realen
Verbrennungsmotoren haben gezeigt, dass eine nach diesem Beispiel ausgebildete
Verschleißschutzschicht auf den Kolbenringen eine völlige Rissfreiheit und ein
annähernd mit galvanisch erzeugten Schichten vergleichbares Verschleißverhalten
aufwies.
Durch die Überlagerung der beiden Schichtwerkstoffe in einer Verschleißschutzschicht
ist es nun möglich, die relativ gute Bearbeitbarkeit der Chrom-Karbide mit der sehr
hohen Verschleißbeständigkeit des Wolfram-Karbids kombinativ zu vereinen. Ein sich
hieraus ergebender Vorteil ist, dass eine Bearbeitung bei völliger Rissfreiheit mit
herkömmlichen Schleifscheiben problemlos möglich ist, dass heißt, eine
Fertigbearbeitung ist nicht kostenintensiver als bei einer herkömmlichen, mittels
heutiger Plasmaspritztechniken erzeugten Verschleißschutzschicht.
Die Cobaltanteile in der Legierung dienen insbesondere als Bindemittel in den
wolframkarbidreichen Bereichen. Die Hartstoffphasen Chrom-Karbid und Wolfram-Karbid
sind die Träger der Härte und bestimmen unter anderem die
Verschleißeigenschaften, während das Bindemetall der Verschleißschutzschicht die
Zähigkeit verleiht.According to the invention, 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. In contrast to the 5 to 50 μm large molybdenum phases known from the prior art, the molybdenum phases are only of a size of not larger than 5 μm, so that there are no wear-increasing phases in the matrix.
In the second, clearly distinguishable layer area, 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 µm and the chrome carbide has a diameter that is smaller than 3 µm, 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.
By superimposing the two layer materials in a wear protection layer, it is now possible to combine the relatively good machinability of the chromium carbide with the very high wear resistance of the tungsten carbide. 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.
Eine erfindungsgemäße Verschleißschutzschicht für einen Kolbenring einer
Verbrennungskraftmaschine ist anhand eines Ausführungsbeispiels in der Zeichnung
dargestellt und wird im weiteren näher erläutert. Es zeigt:
Claims (14)
- Piston ring for internal combustion engines, with a wear protection layer composed of chromium carbides, tungsten carbide, chromium and nickel applied to at least one peripheral surface of the piston ring by means of thermal spray-coating, characterised in that the wear protection layer is formed from a powder mixture, in which the first powder in the form of agglomerated and sintered powder is composed at least of the alloy components chromium carbides, chromium and nickel, and has not been subject to any subsequent embrittling heat treatment such as plasma refining, for example, wherein the carbides in the powder have an average diameter, which is smaller than 3 µm, and a second powder, which is also present in the form of agglomerated and sintered powder and contains tungsten carbide, so that two different layer regions are generated in the wear protection layer, wherein a first region predominantly containing chromium carbide and a second region principally containing tungsten carbide are formed.
- Piston ring according to Claim 1, characterised in that the second powder additionally contains chromium, carbon and nickel, so that during the spray-coating regions high in tungsten carbide are formed, in which predominantly tungsten carbides, chromium carbides and nickel are present.
- Piston ring according to one of Claims 1 and 2, characterised in that the alloy components in the regions high in tungsten carbide are present with amounts of carbon between 8 and 11%, nickel between 6 and 8%, chromium between 18 and 24% and the rest being tungsten.
- Piston ring according to Claim 1, characterised in that the second powder additionally contains nickel, so that during the spray-coating regions high in tungsten carbide are formed, in which predominantly tungsten carbides and nickel are present.
- Piston ring according to one of Claims 1 and 4, characterised in that the alloy components are present with amounts of carbon between 4 and 6%, nickel between 11 and 18% and the rest being tungsten.
- Piston ring according to Claim 1, characterised in that the second powder additionally contains cobalt and chromium, so that during the spray-coating regions high in tungsten carbide are formed, in which predominantly tungsten carbides in a cobalt-chromium alloy are present.
- Piston ring according to one of Claims 1 and 6, characterised in that the alloy components are present with amounts of cobalt between 6 and 18%, chromium between 0.01 and 9% and the rest being tungsten.
- Piston ring according to one of Claims 1 to 7, characterised in that the regions high in chromium carbide contain between 7 and 10% carbon, 10 - 20% nickel, 1-10% molybdenum and the rest being chromium.
- Piston ring according to Claims 1 to 8, characterised in that the proportion of the regions high in tungsten carbide in the mixture amounts to between 1 and 95% by vol.
- Piston ring according to one of Claims 8 to 9, characterised in that the diameters of the phases high in molybdenum in the regions high in chromium carbide are not greater than 5 µm.
- Piston ring according to one of Claims 8 to 10, characterised in that the tungsten carbides on average are not more than 1.5 µm.
- Piston ring according to one of Claims 1 to 11, characterised in that the tungsten carbides are present in the form of WC carbides.
- Piston ring according to one of Claims 1 to 12, characterised in that the chromium carbides are present in the form of Cr3C2 carbides.
- Piston ring according to one of Claims 1 to 13, characterised in that the high-velocity flame spray coating (HVOF) is used as thermal spray coating process.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10061750A DE10061750B4 (en) | 2000-12-12 | 2000-12-12 | Tungsten wear protection layer for piston rings |
| DE10061750 | 2000-12-12 | ||
| PCT/DE2001/004336 WO2002048422A1 (en) | 2000-12-12 | 2001-11-17 | Wear protection layer for piston rings, containing wolfram carbide and chromium carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1341946A1 EP1341946A1 (en) | 2003-09-10 |
| EP1341946B1 true EP1341946B1 (en) | 2004-09-01 |
Family
ID=7666749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01270182A Expired - Lifetime EP1341946B1 (en) | 2000-12-12 | 2001-11-17 | Wear protection layer for piston rings, containing wolfram carbide and chromium carbide |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7001670B2 (en) |
| EP (1) | EP1341946B1 (en) |
| JP (1) | JP4394349B2 (en) |
| AT (1) | ATE275212T1 (en) |
| BR (1) | BR0116079B1 (en) |
| DE (2) | DE10061750B4 (en) |
| WO (1) | WO2002048422A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003273015A1 (en) * | 2002-10-15 | 2004-05-04 | Kabushiki Kaisha Riken | Piston ring and thermal sprayed coating for use therein, and method for manufacture thereof |
| DE102004014871A1 (en) * | 2004-03-26 | 2005-10-13 | Federal-Mogul Burscheid Gmbh | piston ring |
| DE102005020999A1 (en) * | 2005-05-03 | 2006-11-09 | Alfred Flamang | Process for coating components exposed to wear and coated component |
| DE102006049756A1 (en) * | 2006-10-21 | 2008-04-24 | Federal-Mogul Burscheid Gmbh | Wear protection layer for piston rings in combustion engines comprises a layer made from layers of different hardness and metallic phases arranged radially over each other |
| JP5113190B2 (en) * | 2007-01-09 | 2013-01-09 | フェデラル−モーグル ブルシャイト ゲゼルシャフト ミット ベシュレンクテル ハフツング | Piston ring with multilayer coating and process for producing the same |
| US20090191416A1 (en) * | 2008-01-25 | 2009-07-30 | Kermetico Inc. | Method for deposition of cemented carbide coating and related articles |
| DE102008014333B4 (en) | 2008-03-14 | 2012-05-03 | Federal-Mogul Burscheid Gmbh | Wear-resistant component |
| ATE544704T1 (en) * | 2008-07-14 | 2012-02-15 | Sulzer Metco Coatings Gmbh | DIVING POOL ROLL AND METHOD FOR PRODUCING A DIVING POOL ROLL |
| DE102009016650B3 (en) * | 2009-04-07 | 2010-07-29 | Federal-Mogul Burscheid Gmbh | Sliding element with adjustable properties |
| US8906130B2 (en) | 2010-04-19 | 2014-12-09 | Praxair S.T. Technology, Inc. | Coatings and powders, methods of making same, and uses thereof |
| DE102010038289A1 (en) * | 2010-07-22 | 2012-01-26 | Federal-Mogul Burscheid Gmbh | Piston ring with thermal sprayed coating and method of manufacture thereof |
| WO2013062045A1 (en) * | 2011-10-25 | 2013-05-02 | 株式会社Ihi | Piston ring |
| BR102012016283A2 (en) * | 2012-06-29 | 2014-08-12 | Mahle Metal Leve Sa | SLIDING ELEMENT AND INTERNAL COMBUSTION ENGINE |
| US9890858B2 (en) | 2012-06-29 | 2018-02-13 | Mahle Metal Leve S/A | Sliding element and internal combustion engine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB867455A (en) * | 1958-04-24 | 1961-05-10 | Metco Inc | Improvements relating to the production of carbide-containing sprayweld coatings |
| US3606359A (en) * | 1969-08-08 | 1971-09-20 | Ramsey Corp | Tungsten carbide coated piston rings |
| US3837817A (en) * | 1972-10-18 | 1974-09-24 | Nippon Piston Ring Co Ltd | Sliding member having a spray-coated layer |
| US3814447A (en) * | 1972-11-02 | 1974-06-04 | Ramsey Corp | Sealing element for use in internal combustion engines |
| GB1441961A (en) * | 1973-03-21 | 1976-07-07 | Wellworthy Ltd | Piston rings |
| IT1172891B (en) * | 1978-07-04 | 1987-06-18 | Fiat Spa | PROCEDURE FOR COATING A METALLIC SURFACE WITH ANTI-WEAR MATERIAL |
| US4925626A (en) * | 1989-04-13 | 1990-05-15 | Vidhu Anand | Method for producing a Wc-Co-Cr alloy suitable for use as a hard non-corrosive coating |
| US5141571A (en) * | 1991-05-07 | 1992-08-25 | Wall Colmonoy Corporation | Hard surfacing alloy with precipitated bi-metallic tungsten chromium metal carbides and process |
| JPH06117537A (en) * | 1992-10-01 | 1994-04-26 | Hitachi Zosen Corp | Piston ring |
| US5395221A (en) * | 1993-03-18 | 1995-03-07 | Praxair S.T. Technology, Inc. | Carbide or boride coated rotor for a positive displacement motor or pump |
| US5419976A (en) * | 1993-12-08 | 1995-05-30 | Dulin; Bruce E. | Thermal spray powder of tungsten carbide and chromium carbide |
| JPH08210504A (en) * | 1995-01-31 | 1996-08-20 | Nippon Piston Ring Co Ltd | Piston ring |
| CN1079842C (en) * | 1996-03-13 | 2002-02-27 | 株式会社日立制作所 | Runner, water wheel and method of manufacturing the same |
| US5713129A (en) * | 1996-05-16 | 1998-02-03 | Cummins Engine Company, Inc. | Method of manufacturing coated piston ring |
| JP2991977B2 (en) * | 1996-10-04 | 1999-12-20 | トーカロ株式会社 | Conductor roll for electroplating and method of manufacturing the same |
| JPH1150908A (en) * | 1997-07-31 | 1999-02-23 | Nippon Piston Ring Co Ltd | Abrasion resistant sliding member |
| US6071324A (en) * | 1998-05-28 | 2000-06-06 | Sulzer Metco (Us) Inc. | Powder of chromium carbide and nickel chromium |
| JP2001234320A (en) * | 2000-02-17 | 2001-08-31 | Fujimi Inc | Thermal spraying powder material, and thermal spraying method and sprayed coating film using the same |
| DE10046956C2 (en) * | 2000-09-21 | 2002-07-25 | Federal Mogul Burscheid Gmbh | Thermally applied coating for piston rings made of mechanically alloyed powders |
| US6562480B1 (en) * | 2001-01-10 | 2003-05-13 | Dana Corporation | Wear resistant coating for piston rings |
| JP3952252B2 (en) * | 2001-01-25 | 2007-08-01 | 株式会社フジミインコーポレーテッド | Powder for thermal spraying and high-speed flame spraying method using the same |
| US6655181B2 (en) * | 2001-10-15 | 2003-12-02 | General Motors Corporation | Coating for superplastic and quick plastic forming tool and process of using |
-
2000
- 2000-12-12 DE DE10061750A patent/DE10061750B4/en not_active Expired - Fee Related
-
2001
- 2001-11-17 WO PCT/DE2001/004336 patent/WO2002048422A1/en active IP Right Grant
- 2001-11-17 BR BRPI0116079-6A patent/BR0116079B1/en not_active IP Right Cessation
- 2001-11-17 DE DE50103494T patent/DE50103494D1/en not_active Expired - Lifetime
- 2001-11-17 EP EP01270182A patent/EP1341946B1/en not_active Expired - Lifetime
- 2001-11-17 US US10/450,220 patent/US7001670B2/en not_active Expired - Lifetime
- 2001-11-17 JP JP2002550133A patent/JP4394349B2/en not_active Expired - Fee Related
- 2001-11-17 AT AT01270182T patent/ATE275212T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE275212T1 (en) | 2004-09-15 |
| DE10061750B4 (en) | 2004-10-21 |
| WO2002048422A1 (en) | 2002-06-20 |
| JP4394349B2 (en) | 2010-01-06 |
| US7001670B2 (en) | 2006-02-21 |
| BR0116079A (en) | 2003-12-16 |
| DE50103494D1 (en) | 2004-10-07 |
| US20040069141A1 (en) | 2004-04-15 |
| JP2004514795A (en) | 2004-05-20 |
| BR0116079B1 (en) | 2011-04-05 |
| DE10061750A1 (en) | 2002-06-20 |
| EP1341946A1 (en) | 2003-09-10 |
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