EP1507020B1 - Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung - Google Patents

Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung Download PDF

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Publication number
EP1507020B1
EP1507020B1 EP04011394A EP04011394A EP1507020B1 EP 1507020 B1 EP1507020 B1 EP 1507020B1 EP 04011394 A EP04011394 A EP 04011394A EP 04011394 A EP04011394 A EP 04011394A EP 1507020 B1 EP1507020 B1 EP 1507020B1
Authority
EP
European Patent Office
Prior art keywords
powder
weight
coating
gewichts
weight percent
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
EP04011394A
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German (de)
English (en)
French (fr)
Other versions
EP1507020A2 (de
EP1507020A3 (de
Inventor
Gérard BARBEZAT
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.)
Oerlikon Metco AG
Original Assignee
Sulzer Metco AG
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Filing date
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Application filed by Sulzer Metco AG filed Critical Sulzer Metco AG
Publication of EP1507020A2 publication Critical patent/EP1507020A2/de
Publication of EP1507020A3 publication Critical patent/EP1507020A3/de
Application granted granted Critical
Publication of EP1507020B1 publication Critical patent/EP1507020B1/de
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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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
    • B05B7/1404—Arrangements for supplying particulate material
    • B05B7/1431—Arrangements for supplying particulate material comprising means for supplying an additional liquid
    • B05B7/1436—Arrangements for supplying particulate material comprising means for supplying an additional liquid to a container where the particulate material and the additional liquid are brought together
    • 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
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides

Definitions

  • the invention relates to a powder according to claim 1, an applied by plasma spraying iron-containing layer for cylinder surfaces of engine blocks according to claim 4, and a method for producing such layers according to claim 10 or 11.
  • the coating of bores by means of the plasma spraying process has long been known. Different metallic materials can be applied.
  • the layers are finished by diamond honing to the final size and provided with the desired topography.
  • the workability of the layers and the tribological properties are decisively influenced by the microstructure and the physical properties of the corresponding layers.
  • the object of the present invention is to improve the machinability and the tribological properties of plasma-deposited iron-containing layers for cylinder liners of engine blocks.
  • the invention is based on the surprising finding that in a particularly controlled reaction of the powder used with oxygen in plasma spraying, a microstructure can be produced which has excellent properties in terms of machinability and tribology.
  • machinability e.g. the machinability
  • tribology e.g. the friction coefficients and the tendency to scuffing ("scuffing", i.e. the onset of adhesive wear) are drastically reduced.
  • the bound oxygen with iron forms FeO and Fe 3 O 4 crystals.
  • the content of Fe 2 O 3 is less than 0.2% by weight.
  • the amount of oxides formed can be further influenced by mixing the air with nitrogen or oxygen. Replacing the air with pure oxygen reduces the bound level of oxygen in the layer by a factor of about two.
  • a gas amount of 40 to 200 NLPM of oxygen is added.
  • the velocity of the gas flow in the cylinder bore or sleeve during coating is 7 to 12 m / s.
  • the volume of FeO and Fe 3 O 4 can be influenced by selecting the particle size distribution.
  • the particle size of the powder is in the range of 5 to 25 microns, 10 to 45 microns or 15 to 60 microns. It can be determined by means of an optical or electronic microscope, in particular a scanning electron microscope SEM, or by the MICROTRAC laser diffraction method.
  • the oxide ceramic consists of TiO 2 or Al 2 O 3 TiO 2 and / or Al 2 O 3 ZrO 2 alloy systems.
  • the proportion of oxide ceramics in the powder used is preferably 5 to 50% by weight.
  • the choice of the optimum size of the powder particles is made taking into account the tribological properties of the layers produced and the mechanical behavior of the system layer substrate.
  • the particle size of the powder was between 5 to 25 microns, and the preparation was carried out by gas atomization.
  • the velocity of the gas flow during coating of the can was 10 m / s, the amount of air for the layer cooling and powder reaction 500 NLPM (corresponding to 100 NLPM oxygen). This amount of air was supplied through a PlasmatronMech, eg a Plasmatron according to EP-B1-0 645 946 ,
  • the results of the investigations carried out show that the oxygen content in the produced layer is 3% by weight.
  • the oxygen is bound according to investigations by means of X-ray fine structure analysis under the stoichiometric formulas FeO and Fe 3 O 4 . These studies also determined that the formation of Fe 2 O 3 is below the detection limit.
  • Example 1 When using a powder of the same chemical composition as in Example 1, but with a particle size of 10 to 45 microns, and otherwise under the same boundary conditions as in Example 1, the proportion of bound oxygen in the layers produced at 2% by weight. The residual results of analysis of the layer thus applied were the same as in Example 1.
  • the particle size of the powder was between 10 to 45 microns, and the preparation was carried out by gas atomization.
  • Example 2 To the powder according to Example 2, an amount of 30% by weight of an alloyed ceramic powder consisting of 60% by weight of Al 2 O 3 and 40% by weight of TiO 2 was added.
  • the layers produced by means of this powder mixture are mechanically reinforced by the incorporation of the ceramic particles (particle size 5 to 22 ⁇ m).
  • Example 4 Analogously to Example 4, 30% by weight of an alloyed ceramic powder consisting of 80% by weight Al 2 O 3 and 20% by weight ZrO 2 were added. The layers produced by means of this powder mixture are mechanically reinforced by the incorporation of the ceramic particles (particle size 5 to 22 ⁇ m). The same effect as in Example 4 was achieved.
  • Fig. 1 shows a diagram showing the reduction of the friction coefficient as a function of the particle size of the powder and the mechanical behavior, namely the adhesion of the layer on AlSi substrates, depending on the particle size of the powder.
  • the coefficient of friction decreases with increasing size of the particles of the coating powder.
  • the adhesion of the layer to AlSi substrates decreases as the size of the particles of the coating powder increases.
  • a good compromise with regard to the particle size to be chosen can be in the range of 25-30 m, so that a bonding strength of the layer in the range of 45-50 MPa which is sufficient in most precipitates is to be expected, the coefficient of friction, in comparison with layers according to the State of the art, by about 22-25% less. If, however, a very high adhesive strength of the layer is sought in the first place and the reduction of the coefficient of friction is rather of secondary importance, one will select a coating powder with a particle size of less than 25 ⁇ m. On the other hand, if a very low coefficient of friction is sought in the first place and a slightly lower adhesive strength can be accepted, one will choose a coating powder with a particle size of more than 35 m.
  • Figure 2 is a graph showing the reduction of the coefficient of friction as a function of the amount of bound oxygen in the layer and the mechanical behavior, namely the adhesion of the layer to AlSi substrates, as a function of the amount of bound oxygen in the layer evident. From the On the one hand, the diagram clearly shows that the friction coefficient decreases with increasing amount of bound oxygen in the layer. On the other hand, it becomes clear that the adhesion of the layer to AlSi substrates decreases as the amount of bound oxygen in the layer increases.
  • a good compromise with respect to the desired amount of bound oxygen in the layer can be in the range of 2-2.5% by weight, so that in most cases sufficient adhesive strength of the layer in the range of 40-50 MPa is to be expected Coefficient of friction, compared with layers according to the prior art, is about 20-25% less. However, if, as already explained in connection with FIG. 1, primarily a very high adhesive strength of the layer is sought and the reduction of the coefficient of friction is rather of secondary importance, a coating with a proportion of bound oxygen of less than 2 wt aim for%. On the other hand, if a very low coefficient of friction is desired in the first place and a slightly lower adhesive strength can be accepted, one will choose a layer with a bound oxygen content of more than 2.5% by weight.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP04011394A 1999-01-19 1999-12-08 Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung Expired - Lifetime EP1507020B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CH9199 1999-01-19
CH9199 1999-01-19
CH24599 1999-02-09
CH24599 1999-02-09
EP99811122A EP1022351B2 (de) 1999-01-19 1999-12-08 Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP99811122A Division EP1022351B2 (de) 1999-01-19 1999-12-08 Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung

Publications (3)

Publication Number Publication Date
EP1507020A2 EP1507020A2 (de) 2005-02-16
EP1507020A3 EP1507020A3 (de) 2005-04-20
EP1507020B1 true EP1507020B1 (de) 2007-06-27

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EP04011394A Expired - Lifetime EP1507020B1 (de) 1999-01-19 1999-12-08 Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung
EP99811122A Expired - Lifetime EP1022351B2 (de) 1999-01-19 1999-12-08 Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung

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EP99811122A Expired - Lifetime EP1022351B2 (de) 1999-01-19 1999-12-08 Durch Plasmaspritzen aufgebrachte Schicht für Zylinderlaufflächen von Motorblöcken und Verfahren zu deren Herstellung

Country Status (9)

Country Link
US (2) US6548195B1 (es)
EP (2) EP1507020B1 (es)
JP (2) JP3967511B2 (es)
KR (1) KR100593342B1 (es)
AT (2) ATE267275T1 (es)
CA (1) CA2296155C (es)
DE (2) DE59914394D1 (es)
ES (2) ES2221343T5 (es)
PT (2) PT1022351E (es)

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KR101922159B1 (ko) * 2014-11-04 2018-11-27 현대중공업 주식회사 피스톤 스커트부 코팅재 조성물 및 이를 이용한 피스톤 스커트부의 코팅방법
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JP6861217B2 (ja) 2016-02-12 2021-04-21 エリコン サーフェイス ソリューションズ アーゲー，プフェフィコーンＯｅｒｌｉｋｏｎ Ｓｕｒｆａｃｅ Ｓｏｌｕｔｉｏｎｓ ＡＧ，Ｐｆａｆｆｉｋｏｎ トライボロジーシステムとこれを有する内燃エンジン
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JP7159111B2 (ja) * 2019-05-28 2022-10-24 日本ピストンリング株式会社 摺動部材と潤滑油との組み合わせ

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Also Published As

Publication number Publication date
CA2296155E (en) 2000-07-19
US6572931B2 (en) 2003-06-03
PT1507020E (pt) 2007-07-13
ES2221343T5 (es) 2009-06-12
ATE267275T1 (de) 2004-06-15
ES2288232T3 (es) 2008-01-01
JP3967511B2 (ja) 2007-08-29
EP1022351B1 (de) 2004-05-19
JP2000212717A (ja) 2000-08-02
KR20000071238A (ko) 2000-11-25
US6548195B1 (en) 2003-04-15
DE59914394D1 (de) 2007-08-09
US20020051851A1 (en) 2002-05-02
CA2296155A1 (en) 2000-07-19
EP1022351A1 (de) 2000-07-26
EP1507020A2 (de) 2005-02-16
KR100593342B1 (ko) 2006-06-26
EP1507020A3 (de) 2005-04-20
PT1022351E (pt) 2004-10-29
ATE365814T1 (de) 2007-07-15
JP2007191795A (ja) 2007-08-02
JP4644687B2 (ja) 2011-03-02
CA2296155C (en) 2004-09-14
DE59909522D1 (de) 2004-06-24
EP1022351B2 (de) 2009-02-25
ES2221343T3 (es) 2004-12-16

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