EP2459764B1 - Sliding member having a thermally sprayed coating and method for producing same - Google Patents

Sliding member having a thermally sprayed coating and method for producing same Download PDF

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Publication number
EP2459764B1
EP2459764B1 EP10713667.3A EP10713667A EP2459764B1 EP 2459764 B1 EP2459764 B1 EP 2459764B1 EP 10713667 A EP10713667 A EP 10713667A EP 2459764 B1 EP2459764 B1 EP 2459764B1
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EP
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Prior art keywords
percent
weight
recited
sliding member
coating
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EP10713667.3A
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German (de)
French (fr)
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EP2459764A1 (en
Inventor
Marcus Kennedy
Michael Zinnabold
Marc-Manuel Matz
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Federal Mogul Burscheid GmbH
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Federal Mogul Burscheid GmbH
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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

Definitions

  • the present invention relates to a sliding element, in particular a piston ring, for an internal combustion engine, and a manufacturing method for such a sliding element.
  • the aim of the invention is to improve the tribological properties of thermally sprayed piston rings with a previously unused material system as a coating material in comparison to piston ring coatings, which are produced by means of electroplating or thermal spraying.
  • Chromium-based coatings applied by means of thermal spraying, are not yet used on piston rings. Chromium-containing layer systems are nowadays applied to piston rings by means of galvanic processes. In addition, metal oxide or diamond particles are incorporated into the chromium layers during the process to improve wear resistance.
  • EP 0834585 discloses a chromium-based powder.
  • metal oxide or diamond particles reinforced chromium layers which are produced by means of galvanic processes, is the coating of sliding elements with chromium-based materials by means of thermal spraying.
  • the hard material particles are to reduce wear (Cr 3 C 2) in the thermally sprayed layer chromium carbides.
  • a sliding member for an internal combustion engine comprising a substrate and a coating obtainable by thermally spraying a powder comprising the element portions 55-75 weight percent chromium, Cr; 3-10% by weight of silicon, Si; 18-35 weight percent nickel, Ni; 0.1-2 weight percent molybdenum, Mo; 0.1-3 weight percent carbon, C; 0.5-2 weight percent boron, B; and 0-3 weight percent iron, Fe.
  • the material of the sliding element in particular a piston ring, may be, for example, steel or cast iron.
  • the powder comprises Cr 3 C 2 embedded in a Ni / Cr matrix.
  • the particle sizes of the powder are in a range of 5-65 microns.
  • the particle size of carbides embedded in the Ni / Cr matrix is in a range of 1-5 ⁇ m.
  • the layer thickness of the coating is up to 1000 ⁇ m.
  • thermal spraying includes high velocity flame spraying or plasma spraying.
  • the sliding element is a piston ring.
  • a method of manufacturing a sliding element for an internal combustion engine comprising providing a substrate and coating the substrate by thermal spraying a powder comprising the element portions 55-75 weight percent chromium, Cr; 3-10% by weight of silicon, Si; 18-35 weight percent nickel, Ni; 0.1-2 weight percent molybdenum, Mo; 0.1-3 weight percent carbon, C; 0.5-2 weight percent boron, B; and 0-3 weight percent iron, Fe.
  • the powder comprises Cr 3 C 2 embedded in a Ni / Cr matrix.
  • the particle sizes of the powder are in a range of 5-65 microns.
  • the particle size of carbides embedded in the Ni / Cr matrix is in a range of 1-5 ⁇ m.
  • the layer thickness of the coating is up to 1000 ⁇ m.
  • thermal spraying includes high velocity flame spraying or plasma spraying.
  • Table 1 shows the evaluation of the measured wear values in comparison to electroplated Cr-based and thermally sprayed Mo-based layers. It can be clearly seen that the material system described in this invention disclosure as to recognize that the material system described in this invention can be used as an alternative to other coating technologies. In addition, significantly shorter coating times can be achieved by means of the thermal spraying method (100 ⁇ m / min compared to 1 ⁇ m / h for electroplating). Table 1: Evaluation of different coating systems with regard to wear according to standard wear test, based on the maximum wear in the axial direction ring liner Series layer (Cr-based galvanic) (++) (+) Series layer (Mo-based, thermal spraying) (0) (+) Development layer (thermal spraying) (+) (+)

Description

Die vorliegende Erfindung betrifft ein Gleitelement, insbesondere einen Kolbenring, für eine Verbrennungskraftmaschine, sowie ein Herstellungsverfahren für ein solches Gleitelement.The present invention relates to a sliding element, in particular a piston ring, for an internal combustion engine, and a manufacturing method for such a sliding element.

Ziel der Erfindung ist es, die tribologischen Eigenschaften von thermisch gespritzten Kolbenringen mit einem bisher nicht verwendeten Materialsystem als Beschichtungsmaterial im Vergleich zu Kolbenringbeschichtungen, die mittels galvanischer Verfahren oder thermischen Spritzens hergestellt werden, zu verbessern.The aim of the invention is to improve the tribological properties of thermally sprayed piston rings with a previously unused material system as a coating material in comparison to piston ring coatings, which are produced by means of electroplating or thermal spraying.

Chrom-basierte Beschichtungen, aufgetragen mittels thermischen Spritzens, finden noch keine Anwendung auf Kolbenringen. Chromhaltige Schichtsysteme werden heutzutage mittels galvanischer Prozesse auf Kolbenringe aufgetragen. Zusätzlich werden Metalloxid-oder Diamantpartikel während des Prozesses in die Chromschichten eingelagert, um den Verschleißwiderstand zu verbessern. EP 0834585 offenbart ein chrombasiertes Pulver.Chromium-based coatings, applied by means of thermal spraying, are not yet used on piston rings. Chromium-containing layer systems are nowadays applied to piston rings by means of galvanic processes. In addition, metal oxide or diamond particles are incorporated into the chromium layers during the process to improve wear resistance. EP 0834585 discloses a chromium-based powder.

Eine Alternative zu den mit Metalloxid- oder Diamantpartikeln verstärkten Chromschichten, die mittels galvanischer Prozesse hergestellt werden, ist das Beschichten von Gleitelementen mit chrombasierten Materialien mittels thermischen Spritzens. Die Hartstoffpartikel zur Verschleißreduzierung sind bei der thermisch gespritzten Schicht Chromkarbide (Cr3C2).An alternative to the metal oxide or diamond particles reinforced chromium layers, which are produced by means of galvanic processes, is the coating of sliding elements with chromium-based materials by means of thermal spraying. The hard material particles are to reduce wear (Cr 3 C 2) in the thermally sprayed layer chromium carbides.

Die Verwendung von Cr-basierten Schichtsystemen mit Chromkarbiden als Kolbenringbeschichtungsmaterial, hergestellt mittels Plasmaspritzen oder Hochgeschwindigkeits-Flammspritzen (high velocity oxy fuel, HVOF), führt zu der Herstellung eines neuen Kolbenringtyps.The use of Cr-based chromium carbide layer systems as the piston ring coating material produced by plasma spraying or high velocity oxy fuel (HVOF) results in the production of a new type of piston ring.

Gemäß einem ersten Aspekt der Erfindung wird ein Gleitelement für eine Verbrennungskraftmaschine bereitgestellt, umfassend ein Substrat und eine Beschichtung, erhältlich durch thermisches Spritzen eines Pulvers umfassend die Elementanteile
55-75 Gewichtsprozent Chrom, Cr;
3-10 Gewichtsprozent Silizium, Si;
18-35 Gewichtsprozent Nickel, Ni;
0,1-2 Gewichtsprozent Molybdän, Mo;
0,1-3 Gewichtsprozent Kohlenstoff, C;
0,5-2 Gewichtsprozent Bor, B; und
0-3 Gewichtsprozent Eisen, Fe.According to a first aspect of the invention, there is provided a sliding member for an internal combustion engine, comprising a substrate and a coating obtainable by thermally spraying a powder comprising the element portions
55-75 weight percent chromium, Cr;
3-10% by weight of silicon, Si;
18-35 weight percent nickel, Ni;
0.1-2 weight percent molybdenum, Mo;
0.1-3 weight percent carbon, C;
0.5-2 weight percent boron, B; and
0-3 weight percent iron, Fe.

Der Werkstoff des Gleitelements, insbesondere eines Kolbenrings, kann beispielsweise Stahl oder Gusseisen sein.The material of the sliding element, in particular a piston ring, may be, for example, steel or cast iron.

Gemäß einer Ausführungsform weist das Pulver Cr3C2 in einer Ni/Cr-Matrix eingebettet auf.According to one embodiment, the powder comprises Cr 3 C 2 embedded in a Ni / Cr matrix.

Gemäß einer Ausführungsform liegen die Partikelgrößen des Pulvers in einem Bereich von 5-65 µm.In one embodiment, the particle sizes of the powder are in a range of 5-65 microns.

Gemäß einer Ausführungsform liegt die Partikelgröße von in der Ni/Cr-Matrix eingebetteten Karbiden in einem Bereich von 1-5 µm.In one embodiment, the particle size of carbides embedded in the Ni / Cr matrix is in a range of 1-5 μm.

Gemäß einer Ausführungsform beträgt die Schichtdicke der Beschichtung bis zu 1000 µm.According to one embodiment, the layer thickness of the coating is up to 1000 μm.

Gemäß einer Ausführungsform umfasst das thermische Spritzen Hochgeschwindigkeits-Flammspritzen oder Plasmaspritzen.In one embodiment, thermal spraying includes high velocity flame spraying or plasma spraying.

Gemäß einer Ausführungsform ist das Gleitelement ein Kolbenring.According to one embodiment, the sliding element is a piston ring.

Gemäß einem weiteren Aspekt der Erfindung wird ein Verfahren zur Herstellung eines Gleitelements für eine Verbrennungskraftmaschine bereitgestellt, umfassend Bereitstellen eines Substrats und Beschichten des Substrats durch thermisches Spritzen eines Pulvers umfassend die Elementanteile
55-75 Gewichtsprozent Chrom, Cr;
3-10 Gewichtsprozent Silizium, Si;
18-35 Gewichtsprozent Nickel, Ni;
0,1-2 Gewichtsprozent Molybdän, Mo;
0,1-3 Gewichtsprozent Kohlenstoff, C;
0,5-2 Gewichtsprozent Bor, B; und
0-3 Gewichtsprozent Eisen, Fe.According to another aspect of the invention, there is provided a method of manufacturing a sliding element for an internal combustion engine, comprising providing a substrate and coating the substrate by thermal spraying a powder comprising the element portions
55-75 weight percent chromium, Cr;
3-10% by weight of silicon, Si;
18-35 weight percent nickel, Ni;
0.1-2 weight percent molybdenum, Mo;
0.1-3 weight percent carbon, C;
0.5-2 weight percent boron, B; and
0-3 weight percent iron, Fe.

Gemäß einer Ausführungsform weist das Pulver Cr3C2 in einer Ni/Cr-Matrix eingebettet auf.According to one embodiment, the powder comprises Cr 3 C 2 embedded in a Ni / Cr matrix.

Gemäß einer Ausführungsform liegen die Partikelgrößen des Pulvers in einem Bereich von 5-65 µm.In one embodiment, the particle sizes of the powder are in a range of 5-65 microns.

Gemäß einer Ausführungsform liegt die Partikelgröße von in der Ni/Cr-Matrix eingebetteten Karbiden in einem Bereich von 1-5 µm.In one embodiment, the particle size of carbides embedded in the Ni / Cr matrix is in a range of 1-5 μm.

Gemäß einer Ausführungsform beträgt die Schichtdicke der Beschichtung bis zu 1000 µm.According to one embodiment, the layer thickness of the coating is up to 1000 μm.

Gemäß einer Ausführungsform umfasst das thermische Spritzen Hochgeschwindigkeits-Flammspritzen oder Plasmaspritzen.In one embodiment, thermal spraying includes high velocity flame spraying or plasma spraying.

Kurze Beschreibung der ZeichnungShort description of the drawing

Fig. 1Fig. 1
zeigt eine Abbildung der Mikrostruktur einer Cr-Ni-Si-C-Fe-B-Beschichtung auf Kolbenringmaterial, hergestellt mittels HVOF, die nicht unter Anspruch 1 fällt.FIG. 4 shows an illustration of the microstructure of a Cr-Ni-Si-C-Fe-B coating on piston ring material made by means of HVOF, which does not fall under claim 1.

Das Pulver wurde verspritzt und die Mikrostruktur (gezeigt in Fig. 1) sowie Härte und Verschleißeigenschaften geprüft. Die Mikrostrukturaufnahmen zeigen homogen verteilte Karbide, keine unaufgeschmolzenen Partikel und eine sehr dichte Schicht mit einer geringen Porösität. Das hierbei verwendete Materialsystem hat folgende chemische Zusammensetzung ergeben:

  • 65,5 - 65,7 Gewichtsprozent Chrom, Cr;
  • 3,7 - 3,9 Gewichtsprozent Silizium, Si;
  • 21,2 - 21,4 Gewichtsprozent Nickel, Ni;
  • 1,2 - 1,3 Gewichtsprozent Molybdän, Mo;
  • 5,8 - 5,9 Gewichtsprozent Kohlenstoff, C;
  • 0,7 Gewichtsprozent Bor, B; und
  • 1,2 Gewichtsprozent Eisen, Fe;
The powder was sprayed and the microstructure (shown in Fig. 1 ) as well as hardness and wear properties. The microstructural images show homogeneously distributed carbides, no unmelted particles and a very dense layer with a low porosity. The material system used has the following chemical composition:
  • 65.5-65.7 weight percent chromium, Cr;
  • 3.7 - 3.9 weight percent silicon, Si;
  • 21.2-21.4 weight percent nickel, Ni;
  • 1.2-1.3 weight percent molybdenum, Mo;
  • 5.8-5.9 weight percent carbon, C;
  • 0.7 weight percent boron, B; and
  • 1.2 weight percent iron, Fe;

Erste Versuche haben gezeigt, dass die Schichten eine Porosität von < 5% bei einer Härte von etwa 948 HV0.1 aufweisen. Dies wird durch die vorhandenen Hartstoffphasen wie Cr3Si, Ni2Si, Fe3B sowie Cr5B3 sowie den HVOF Prozess verursacht.Initial tests have shown that the layers have a porosity of <5% at a hardness of about 948 HV0.1. This is caused by the existing hard material phases such as Cr 3 Si, Ni 2 Si, Fe 3 B and Cr 5 B 3 as well as the HVOF process.

Um die tribologischen Eigenschaften dieses Systems zu prüfen, wurden Verschleißtests auf dem internen Standard-Prüfsystem im geschmierten Zustand durchgeführt.To test the tribological properties of this system, wear tests were performed on the internal standard test system in the lubricated state.

Tabelle 1 zeigt die Bewertung der gemessenen Verschleißwerte im Vergleich zu galvanisch hergestellten Cr-basierten und thermisch gespritzten Mo-basierten Schichten. Es ist deutlich zu erkennen, dass das in dieser Erfindungsmeldung beschriebene Materialsystem als zu erkennen, dass das in dieser Erfindungsmeldung beschriebene Materialsystem als Alternative gegenüber anderen Beschichtungstechnologien verwendet werden kann. Zudem sind mittels des thermischen Spritzverfahrens wesentlich kürzere Beschichtungszeiten realisierbar (100 µm/min gegenüber 1 µm/h für Galvanik). Tabelle 1: Bewertung unterschiedlicher Schichtsysteme hinsichtlich Verschleiß nach Standard-Verschleißtest, bezogen auf den maximalen Verschleiß in axialer Richtung Ring Laufbuchse Serienschicht (Cr-basiert galvanisch) (++) (+) Serienschicht (Mo-basiert, thermisches Spritzen) (0) (+) Entwicklungsschicht (thermisches Spritzen) (+) (+) Table 1 shows the evaluation of the measured wear values in comparison to electroplated Cr-based and thermally sprayed Mo-based layers. It can be clearly seen that the material system described in this invention disclosure as to recognize that the material system described in this invention can be used as an alternative to other coating technologies. In addition, significantly shorter coating times can be achieved by means of the thermal spraying method (100 μm / min compared to 1 μm / h for electroplating). Table 1: Evaluation of different coating systems with regard to wear according to standard wear test, based on the maximum wear in the axial direction ring liner Series layer (Cr-based galvanic) (++) (+) Series layer (Mo-based, thermal spraying) (0) (+) Development layer (thermal spraying) (+) (+)

Claims (13)

  1. A sliding member for an internal combustion engine, comprising
    - a substrate; and
    - a coating, obtainable by thermal spraying of a powder including the element proportions
    55-75 percent by weight chromium, Cr;
    3-10 percent by weight silicon, Si;
    18-35 percent by weight nickel, Ni;
    0.1-2 percent by weight molybdenum, Mo;
    0.1-3 percent by weight carbon, C;
    0.5-2 percent by weight boron, B; and
    0-3 percent by weight iron, Fe.
  2. The sliding member as recited in claim 1, wherein the powder includes Cr3C2 embedded in a Ni/Cr matrix.
  3. The sliding member as recited in any of claims 1 to 2, wherein the particle sizes of the powder are in a range from 5-65 µm.
  4. The sliding member as recited in any of claims 1 to 3, wherein the particle size of carbides embedded in the Ni/Cr matrix is in a range from 1-5 µm.
  5. The sliding member as recited in any of claims 1 to 4, wherein the layer thickness of the coating is up to 1000 µm.
  6. The sliding member as recited in any of claims 1 to 5, wherein the thermal spraying method includes high velocity oxy fuel spraying or plasma spraying.
  7. The sliding member as recited in any of claims 1 to 6, wherein the sliding member is a piston ring.
  8. A method for producing a sliding member for an internal combustion engine, comprising
    - providing a substrate; and
    - coating the substrate by thermal spraying of a powder including the element proportions
    55-75 percent by weight chromium, Cr;
    3-10 percent by weight silicon, Si;
    18-35 percent by weight nickel, Ni;
    0.1-2 percent by weight molybdenum, Mo;
    0.1-3 percent by weight carbon, C;
    0.5-2 percent by weight boron, B; and
    0-3 percent by weight iron, Fe.
  9. The method as recited in claim 8, wherein the powder includes Cr3C2 embedded in a Ni/Cr matrix.
  10. The method as recited in any of claims 8 to 9, wherein the particle sizes of the powder are in a range from 5-65 µm.
  11. The method as recited in any of claims 8 to 10, wherein the particle size of carbides embedded in the Ni/Cr matrix is in a range from 1-5 µm.
  12. The method as recited in any of claims 8 to 11, wherein the layer thickness of the coating is up to 1000 µm.
  13. The method as recited in any of claims 8 to 12, wherein the thermal spraying includes high velocity oxy fuel spraying or plasma spraying.
EP10713667.3A 2009-07-29 2010-04-15 Sliding member having a thermally sprayed coating and method for producing same Active EP2459764B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009035210A DE102009035210B3 (en) 2009-07-29 2009-07-29 Sliding element with thermally sprayed coating and manufacturing method therefor
PCT/EP2010/054961 WO2011012336A1 (en) 2009-07-29 2010-04-15 Sliding member having a thermally sprayed coating and method for producing same

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EP2459764A1 EP2459764A1 (en) 2012-06-06
EP2459764B1 true EP2459764B1 (en) 2014-12-10

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US (1) US8827276B2 (en)
EP (1) EP2459764B1 (en)
JP (1) JP5668063B2 (en)
KR (1) KR101718840B1 (en)
CN (1) CN102471862B (en)
BR (1) BR112012000073A2 (en)
DE (1) DE102009035210B3 (en)
PT (1) PT2459764E (en)
RU (1) RU2516105C2 (en)
WO (1) WO2011012336A1 (en)

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RU2516105C2 (en) 2014-05-20
RU2012105338A (en) 2013-09-10
JP2013500392A (en) 2013-01-07
JP5668063B2 (en) 2015-02-12
WO2011012336A1 (en) 2011-02-03
CN102471862B (en) 2014-10-22
DE102009035210B3 (en) 2010-11-25
US20120126487A1 (en) 2012-05-24
US8827276B2 (en) 2014-09-09
CN102471862A (en) 2012-05-23
PT2459764E (en) 2015-02-24
EP2459764A1 (en) 2012-06-06
KR101718840B1 (en) 2017-03-22
KR20120055575A (en) 2012-05-31
BR112012000073A2 (en) 2017-05-09

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