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EP1559808A1 - Iron containing coating applied by thermal spraying on a sliding surface,especially on cylinder boxes of engine blocks - Google Patents

Iron containing coating applied by thermal spraying on a sliding surface,especially on cylinder boxes of engine blocks Download PDF

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Publication number
EP1559808A1
EP1559808A1 EP05100596A EP05100596A EP1559808A1 EP 1559808 A1 EP1559808 A1 EP 1559808A1 EP 05100596 A EP05100596 A EP 05100596A EP 05100596 A EP05100596 A EP 05100596A EP 1559808 A1 EP1559808 A1 EP 1559808A1
Authority
EP
European Patent Office
Prior art keywords
iron
containing layer
weight
thermal spraying
sliding surface
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.)
Withdrawn
Application number
EP05100596A
Other languages
German (de)
French (fr)
Inventor
Clemens Verpoort
Maik Broda
Daniel J. Branagan
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.)
Ford Global Technologies LLC
Original Assignee
Ford Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ford Global Technologies LLC filed Critical Ford Global Technologies LLC
Publication of EP1559808A1 publication Critical patent/EP1559808A1/en
Withdrawn legal-status Critical Current

Links

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
    • C23C4/18—After-treatment
    • 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
    • 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 invention relates to an applied by thermal spraying ferrous Layer of a sliding surface, in particular for cylinder surfaces of engine blocks according to the preamble of claim 1 and a process for the preparation and a use.
  • the iron-containing layer an amorphous structure with finely divided, nano-crystalline Has metal borides and / or metal carbides, is the sliding surface heavy duty because of the nano-crystalline precipitations of the metal borides and metal carbides creates a layer of extremely high hardness.
  • the borides cause a very low coefficient of friction, so this layer too has excellent sliding properties.
  • Preferred application are highly loaded cylinder surfaces of supercharged diesel and gasoline engines. Due to the high mechanical clasping of the layer with the Base material, the coating is particularly suitable for thermal shock stressed engines. Thermal shock occurs when at cold start at low Ambient temperatures Engines quickly under load to maximum speed to turn up.
  • the high iron content of greater than 60% in conjunction with the metalloids boron, carbon and silicon on application causes the amorphous structure of the iron-containing layer by the liquid melt droplets solidify at a very high cooling rate of about 10 5 -10 6 Kelvin per second.
  • nano-crystalline precipitates are formed from this amorphous matrix, whereby the high hardness arises.
  • the layer preferably has a thickness of 100 ⁇ m to 2 mm. Depending on the thickness results in a different hardness, in principle, the hardness with increasing thickness of the Layer becomes larger, since at several spray layers, in which material is applied becomes, it to the increased excretion of the nano-crystalline carbides or borides comes.
  • the iron-containing layer has a hardness of 1000 to 1250 HV 0.05,
  • the hardness by appropriate process parameters and Material composition readily in the range between 800 HV 0.05 and 1500 HV 0.05 can be adjusted.
  • Such hardness is currently z. B. at Carbide tools based on tungsten carbide / cobalt known, and can now also be used extensively for sliding surfaces. Because of the high Hardness is the iron-containing layer extremely resistant to wear.
  • the metal borides or metal carbides preferably have a size of 60 to 130 nm. Due to the small size, the friction is reduced and the Hardness increased.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Sliding-Contact Bearings (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

Sliding surfaces, and especially motor block cylinder surfaces, are layers with a ferrous content applied by thermal spraying. The applied layer also contains non-metal elements, in an amorphous structure with finely-distributed nano-crystalline metal borides and/or metal carbides in dimensions of 60-130 nm. The applied layer has a thickness of 100 mu m to 2 mm and a hardness of 1000-1250 HV 0.05.

Description

Die Erfindung betrifft eine durch thermisches Spritzen aufgebrachte eisenhaltige Schicht einer Gleitfläche, insbesondere für Zylinderlaufflächen von Motorblöcken nach dem Oberbegriff des Anspruches 1 und ein Verfahren zur Herstellung sowie eine Verwendung.The invention relates to an applied by thermal spraying ferrous Layer of a sliding surface, in particular for cylinder surfaces of engine blocks according to the preamble of claim 1 and a process for the preparation and a use.

Aus der EP 0858519 ist eine gattungsbildende eisenhaltige Schicht bekannt. Dabei wird eine Eisen-Molybdän-Legierung durch thermisches Spritzen auf eine metallische Oberfläche aufgetragen. Eine Schicht weist einen sehr geringen Reibungskoeffizient auf. Jedoch kann mit dieser Schicht maximal eine Härte von 850 HV 0,05 erreicht werden, und die Schicht ist durch den hohen Molybdänanteil in der Herstellung sehr teuer.From EP 0858519 a generic iron-containing layer is known. there is an iron-molybdenum alloy by thermal spraying on a applied metallic surface. One layer has a very small one Friction coefficient on. However, with this layer a maximum hardness of 850 HV 0.05, and the layer is due to the high molybdenum content in the production very expensive.

Demgemäß ist es die Aufgabe der Erfindung, eine eisenhaltige Schicht so zu verbessern, daß eine Härte höher als 850 HV 0,05 erreicht werden kann bei möglichst guten Reibungseigenschaften und geringeren Herstellungskosten.Accordingly, it is the object of the invention to provide an iron-containing layer so improve that a hardness higher than 850 HV 0.05 can be achieved at the best possible friction properties and lower production costs.

Gelöst wird diese Aufgabe mit den Merkmalen des Anspruches 1.This problem is solved with the features of claim 1.

Indem die eisenhaltige Schicht eine amorphe Struktur mit feinverteilten, nano-kristallinen Metallboriden und / oder Metallkarbiden aufweist, ist die Gleitfläche hochbelastbar, da aufgrund der nano-kristallinen Ausscheidungen der Metallboride und Metallkarbide eine Schicht mit extrem hoher Härte entsteht. Weiterhin führen die Boride zu einem sehr geringen Reibungskoeffizient, so daß diese Schicht auch hervorragende Gleiteigenschaften aufweist. Bevorzugte Anwendung sind hochbelastete Zylinderlaufflächen von aufgeladenen Diesel- und Benzinmotoren. Aufgrund der hohen mechanischen Umklammerung der Schicht mit dem Grundmaterial eignet sich die Beschichtung insbesondere auch für Thermoschock beanspruchte Motoren. Thermoschock tritt auf, wenn beim Kaltstart bei niedrigen Umgebungstemperaturen Motoren schnell unter Last auf Höchstdrehzahl hochdrehen.By the iron-containing layer an amorphous structure with finely divided, nano-crystalline Has metal borides and / or metal carbides, is the sliding surface heavy duty because of the nano-crystalline precipitations of the metal borides and metal carbides creates a layer of extremely high hardness. Continue to lead the borides cause a very low coefficient of friction, so this layer too has excellent sliding properties. Preferred application are highly loaded cylinder surfaces of supercharged diesel and gasoline engines. Due to the high mechanical clasping of the layer with the Base material, the coating is particularly suitable for thermal shock stressed engines. Thermal shock occurs when at cold start at low Ambient temperatures Engines quickly under load to maximum speed to turn up.

Bevorzugt weist die eisenhaltige Schicht folgende Zusammensetzung auf, wobei zumindest folgende Elemente mit dem angegebenen Gewichtsanteilen Bestandteil der Schicht sind:

  • Eisen mit 60 bis 97 Gew.-%,
  • Chrom 1 bis 20 Gew.-%,
  • Wolfram 0,5 bis 5 Gew.-%,
  • Molybdän 0,5 - 5 Gew.-%,
  • Mangan 0,2 - 20 Gew.-%,
  • Bor 0,2 - 5 Gew.%,
  • Kohlenstoff 0,2 - 5 Gew.-%, und
  • Silizium 0,2 - 5 Gew.-%.
    • The iron-containing layer preferably has the following composition, wherein at least the following elements with the stated proportions by weight are part of the layer:
  • Iron with 60 to 97 wt .-%,
  • Chromium 1 to 20% by weight,
  • Tungsten 0.5 to 5% by weight,
  • Molybdenum 0.5 to 5% by weight,
  • Manganese 0.2-20% by weight,
  • Boron 0.2-5% by weight,
  • Carbon 0.2 - 5 wt .-%, and
  • Silicon 0.2 to 5 wt .-%.

    • Insbesondere der hohe Eisenanteil von größer 60 % in Verbindung mit den Metalloiden Bor, Kohlenstoff und Silizum bewirkt beim Auftragen die amorphe Struktur der eisenhaltigen Schicht, indem die flüssigen Schmelztropfen mit einer sehr hohen Abkühlgeschwindigkeit von etwa 105-106 Kelvin pro Sekunde erstarren. Bei dem nachfolgenden Auftreffen weiterer flüssiger Spritzpartikel werden aus dieser amorphen Matrix nano-kristalline Ausscheidungen gebildet, wodurch die hohe Härte entsteht.In particular, the high iron content of greater than 60% in conjunction with the metalloids boron, carbon and silicon on application causes the amorphous structure of the iron-containing layer by the liquid melt droplets solidify at a very high cooling rate of about 10 5 -10 6 Kelvin per second. In the subsequent impact of other liquid spray particles nano-crystalline precipitates are formed from this amorphous matrix, whereby the high hardness arises.

    Bevorzugt weist die Schicht eine Dicke von 100 µm bis 2 mm auf. Je nach Dicke ergibt sich eine andere Härte, wobei prinzipiell die Härte mit zunehmender Dicke der Schicht größer wird, da bei mehreren Spritzlagen, in denen Material aufgetragen wird, es zur vermehrten Ausscheidung der nano-kristallinen Karbide bzw. Boride kommt.The layer preferably has a thickness of 100 μm to 2 mm. Depending on the thickness results in a different hardness, in principle, the hardness with increasing thickness of the Layer becomes larger, since at several spray layers, in which material is applied becomes, it to the increased excretion of the nano-crystalline carbides or borides comes.

    Bevorzugt weist die eisenhaltige Schicht eine Härte von 1000 bis 1250 HV 0,05 auf, jedoch kann die Härte durch entsprechende Prozeßparameter und Materialzusammensetzung ohne weiteres im Bereich zwischen 800 HV 0,05 und 1500 HV 0,05 eingestellt werden. Eine solche Härte ist bisher z. B. bei Hartmetallwerkzeugen auf Basis von Wolfram-Karbid / Kobalt bekannt, und kann jetzt auch für Gleitflächen großflächig angewendet werden. Aufgrund der hohen Härte ist die eisenhaltige Schicht extrem verschleißfest.Preferably, the iron-containing layer has a hardness of 1000 to 1250 HV 0.05, However, the hardness by appropriate process parameters and Material composition readily in the range between 800 HV 0.05 and 1500 HV 0.05 can be adjusted. Such hardness is currently z. B. at Carbide tools based on tungsten carbide / cobalt known, and can now also be used extensively for sliding surfaces. Because of the high Hardness is the iron-containing layer extremely resistant to wear.

    Bevorzugt weisen die Metallboride bzw. Metallkarbide eine Größe von 60 bis 130 nm aufweisen. Aufgrund der geringen Größe wird die Reibung reduziert und die Härte gesteigert.The metal borides or metal carbides preferably have a size of 60 to 130 nm. Due to the small size, the friction is reduced and the Hardness increased.

    Claims (5)

    Durch thermisches Spritzen aufgebrachte eisenhaltige Schicht einer Gleitfläche, insbesondere für Zylinderlaufflächen von Motorblöcken, wobei die eisenhaltige Schicht weitere metallische, metalloide und/oder nichtmetallische Elemente beinhaltet,
    dadurch gekennzeichnet, daß
    die eisenhaltige Schicht eine amorphe Struktur mit feinverteilten, nano-kristallinen Metallboriden und / oder Metallkarbiden aufweist.    An iron-containing layer of a sliding surface applied by thermal spraying, in particular for cylinder running surfaces of engine blocks, wherein the iron-containing layer contains further metallic, metalloid and / or non-metallic elements,
    characterized in that
    the iron-containing layer has an amorphous structure with finely divided, nano-crystalline metal borides and / or metal carbides.         Eisenhaltige Schicht nach Anspruch 1,
    dadurch gekennzeichnet, daß
    zumindest folgende Elemente mit dem angegebenen Gewichtsanteilen Bestandteil der Schicht sind: Eisen mit 60 bis 97 Gew.-%, Chrom 1 bis 20 Gew.-%, Wolfram 0,5 bis 5 Gew.-%, Molybdän 0,5 - 5 Gew.-%, Mangan 0,2 - 20 Gew.-%, Bor 0,2 - 5 Gew.%, Kohlenstoff 0,2 - 5 Gew.-%, und Silizium 0,2 - 5 Gew.-%.     Iron-containing layer according to claim 1,
    characterized in that
    at least the following elements with the stated parts by weight of the layer are: Iron with 60 to 97 wt .-%, Chromium 1 to 20% by weight, Tungsten 0.5 to 5% by weight, Molybdenum 0.5 to 5% by weight, Manganese 0.2-20% by weight, Boron 0.2-5% by weight, Carbon 0.2 - 5 wt .-%, and Silicon 0.2 to 5 wt .-%.     Eisenhaltige Schicht nach Anspruch 1 oder 2,
    dadurch gekennzeichnet, daß
    die Schicht eine Dicke von 100 µm bis 2 mm aufweist.    Iron-containing layer according to claim 1 or 2,
    characterized in that
    the layer has a thickness of 100 microns to 2 mm.         Eisenhaltige Schicht nach einem der vorherigen Ansprüche,
    dadurch gekennzeichnet, daß
    die eisenhaltige Schicht eine Härte von 1000 bis 1250 HV 0,05 aufweist.     Iron-containing layer according to one of the preceding claims,
    characterized in that
    the iron-containing layer has a hardness of 1000 to 1250 HV 0.05.         Eisenhaltige Schicht nach einem der vorherigen Ansprüche,
    dadurch gekennzeichnet, daß
    die Metallboride bzw. Metallkarbide eine Größe von 60 bis 130 nm aufweisen.    Iron-containing layer according to one of the preceding claims,
    characterized in that
    the metal borides or metal carbides have a size of 60 to 130 nm.
    EP05100596A 2004-01-28 2005-01-28 Iron containing coating applied by thermal spraying on a sliding surface,especially on cylinder boxes of engine blocks Withdrawn EP1559808A1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE102004004457 2004-01-28
    DE102004004457 2004-01-28

    Publications (1)

    Publication Number Publication Date
    EP1559808A1 true EP1559808A1 (en) 2005-08-03

    Family

    ID=34638796

    Family Applications (4)

    Application Number Title Priority Date Filing Date
    EP05100575A Withdrawn EP1559806A1 (en) 2004-01-28 2005-01-28 Iron containing coating applied by thermal spraying on a sliding surface,especially on cylinder bores of engine blocks
    EP05707873A Expired - Lifetime EP1711642B1 (en) 2004-01-28 2005-01-28 Ferrous layer for a sliding surface, in particular for cylinder running surfaces on engine blocks, applied by means of thermal spraying
    EP05100596A Withdrawn EP1559808A1 (en) 2004-01-28 2005-01-28 Iron containing coating applied by thermal spraying on a sliding surface,especially on cylinder boxes of engine blocks
    EP05100597A Withdrawn EP1559807A1 (en) 2004-01-28 2005-01-28 Method of repairing worn sliding surfaces, especially cylinder bores of engine blocks

    Family Applications Before (2)

    Application Number Title Priority Date Filing Date
    EP05100575A Withdrawn EP1559806A1 (en) 2004-01-28 2005-01-28 Iron containing coating applied by thermal spraying on a sliding surface,especially on cylinder bores of engine blocks
    EP05707873A Expired - Lifetime EP1711642B1 (en) 2004-01-28 2005-01-28 Ferrous layer for a sliding surface, in particular for cylinder running surfaces on engine blocks, applied by means of thermal spraying

    Family Applications After (1)

    Application Number Title Priority Date Filing Date
    EP05100597A Withdrawn EP1559807A1 (en) 2004-01-28 2005-01-28 Method of repairing worn sliding surfaces, especially cylinder bores of engine blocks

    Country Status (4)

    Country Link
    EP (4) EP1559806A1 (en)
    AT (1) ATE473311T1 (en)
    DE (1) DE502005009857D1 (en)
    WO (1) WO2005073425A1 (en)

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    DE102008019933A1 (en) 2008-04-21 2009-10-22 Ford Global Technologies, LLC, Dearborn Apparatus and method for preparing a metal surface for applying a thermally sprayed layer
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    Publication number Priority date Publication date Assignee Title
    DE102005063123B3 (en) * 2005-12-30 2007-05-31 Federal-Mogul Burscheid Gmbh Piston ring for sealing chamber in cylinder has running-in layer containing hydrogen and nanocrystalline carbide phases
    US8201831B2 (en) 2005-12-30 2012-06-19 Federal-Mogul Burscheid Gmbh Sliding element, in particular piston ring, method for manufacturing a sliding element, sliding system and coating for a sliding element

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    EP1711642A1 (en) 2006-10-18
    EP1559806A1 (en) 2005-08-03
    EP1559807A1 (en) 2005-08-03
    WO2005073425A1 (en) 2005-08-11
    ATE473311T1 (en) 2010-07-15
    EP1711642B1 (en) 2010-07-07
    DE502005009857D1 (en) 2010-08-19

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