EP1967601B1 - Method for manufacturing a coating - Google Patents

Method for manufacturing a coating Download PDF

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Publication number
EP1967601B1
EP1967601B1 EP08002244.5A EP08002244A EP1967601B1 EP 1967601 B1 EP1967601 B1 EP 1967601B1 EP 08002244 A EP08002244 A EP 08002244A EP 1967601 B1 EP1967601 B1 EP 1967601B1
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EP
European Patent Office
Prior art keywords
iron alloy
boron carbide
coating
arc wire
iron
Prior art date
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Active
Application number
EP08002244.5A
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German (de)
French (fr)
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EP1967601A3 (en
EP1967601A2 (en
Inventor
Martin Walter
Wolfram Dr. Wagener
Klaus Daiker
Markus Wittmann
Goetz Mielsch
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.)
Bayerische Motoren Werke AG
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Bayerische Motoren Werke AG
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Publication of EP1967601A2 publication Critical patent/EP1967601A2/en
Publication of EP1967601A3 publication Critical patent/EP1967601A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • 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
    • 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
    • C23C4/131—Wire arc spraying

Definitions

  • the known coating does not meet the corrosion requirements that are to be placed on an internal combustion engine. In addition, it has a tensile stress, which leads to local delamination and thus the failure of the coating in operation.
  • the coating of the invention meets all corrosion requirements that are placed on an engine block made of aluminum or the like light metal, in particular against salt and sulfur corrosion, especially in fuels with increased sulfur content, eg. B. Venezuela fuel.
  • the boron carbide is at least partially converted to iron boride (Fe x B x ) in the iron alloy molten during arc wire spraying, thereby hardening the coating and substantially increasing its wear resistance.
  • iron boride Fe x B x
  • the boron carbide is preferably used with a particle size of 0.1 to 10 microns.
  • two wires which consist of the iron alloy used in the invention, fed to a spray head, such that a current transmission to the wires, wherein the two wires touch with its end, whereby an arc is formed by a permanent short circuit, the wires melting at the end.
  • Behind the melt zone is a nozzle from which compressed air or an inert gas, such as nitrogen, exits. This gas stream atomizes the molten iron alloy and supplies it to the surface to be coated.
  • a melting head is used, which has a feed into the gas stream upstream of the arc for the boron carbide.
  • the cylinder liners of an internal combustion engine are preferably pretreated with a high-pressure water jet before coating.
  • the spray head is inserted into one of the cylinders, wherein it rotates during spraying around the cylinder longitudinal axis.
  • the applied to the cylinder bore by thermal spraying layer for example, has a layer thickness of 0.2 to 0.6 mm.
  • By honing and the like finish finally, for example, a 0.1 to 0.2 mm thick cylinder liner coating is obtained.
  • FIGURE of which shows a side view of a lance for the LDS method with a longitudinally cut extrusion head.
  • a spray head 2 is attached to a lance 1.
  • a lance 1 As shown by the arrows 3 and 4, two wires 5, 6 introduced from the iron alloy according to the invention, which are transported to the spray head 2, from which they emerge so that they touch with their ends 7, 8 , The wires 5, 6 are energized with contacts, not shown, so that forms an arc and thus a melting zone 9 at their ends 7, 8 by a short circuit.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung einer Beschichtung durch Lichtbogendrahtspritzen und eine nach dem Verfahren hergestellte Beschichtung. Sie hat ferner eine Vorrichtung zur Durchführung des Verfahrens zum Gegenstand.The invention relates to a method for producing a coating by arc wire spraying and a coating produced by the method. It also has an apparatus for carrying out the method of the subject.

Um bei einem Aluminium-Motorblock für eine widerstandsfähige Oberfläche der Zylinderlaufbahn zu sorgen, ist es bekannt, die Zylinderlaufbahn mit einer Eisenbeschichtung durch Lichtbogendrahtspritzen mit einem Eisendraht zu versehen.In order to provide a durable surface of the cylinder bore in an aluminum engine block, it is known to provide the cylinder bore with an iron coating by arc wire spraying with an iron wire.

Die bekannte Beschichtung erfüllt jedoch nicht die Korrosionsanforderungen, die an einen Verbrennungsmotor zu stellen sind. Zudem weist sie eine Zugspannung auf, die zu lokalen Enthaftungen und damit zum Versagen der Beschichtung im Betrieb führt.However, the known coating does not meet the corrosion requirements that are to be placed on an internal combustion engine. In addition, it has a tensile stress, which leads to local delamination and thus the failure of the coating in operation.

Aus DE 10306919 B4 und EP 0 246 596 B1 ist es bekannt, zum Lichtbogendrahtspritzen einen Verbundstoffdracht aus einer Eisenlegierung und Borcarbid zu verwenden.Out DE 10306919 B4 and EP 0 246 596 B1 It is known to use an iron alloy composite and boron carbide for arc wire spraying.

Aufgabe der Erfindung ist es daher, eine Beschichtung, insbesondere für die Zylinderlaufbahn von Aluminium-Motorblöcken bereitzustellen, die sich neben einer hohen Verschleißbeständigkeit durch eine hohe Korrosionsfestigkeit und feste Haftung auszeichnet.The object of the invention is therefore to provide a coating, in particular for the cylinder bore of aluminum engine blocks, which is characterized in addition to a high wear resistance by a high corrosion resistance and firm adhesion.

Dies wird erfindungsgemäß durch das im Anspruch 1 gekennzeichnete Verfahren erreicht.This is inventively achieved by the method characterized in claim 1.

Nach der Erfindung wird zum Lichtbogendrahtspritzen eine Eisenlegierung verwendet, die 5 bis 25, vorzugsweise 10 bis 18 Gew.% Chrom und 0,5 bis 5, vorzugsweise 0,8 bis 3 Gew.% Molybdän enthält. Gleichzeitig wird beim Lichtbogendrahtspritzen der zu beschichtenden Oberfläche zusammen mit der geschmolzenen Eisenlegierung Borcarbid (B4C) zugeführt. Dabei beträgt der Anteil des Borcarbids, der beim Lichtbogendrahtspritzen zugeführt wird, 0,5 bis 8, vorzugsweise 1 bis 5 Gew.%, sodass der Anteil der Eisenlegierung 92 bis 99,5 bzw. 95 bis 99 Gew.% ausmacht.According to the invention, an iron alloy is used for the arc wire spraying, the 5 to 25, preferably 10 to 18 wt.% Chromium and 0.5 to 5, preferably 0.8 to 3 wt.% Contains molybdenum. At the same time, during arc wire spraying, boron carbide (B 4 C) is supplied to the surface to be coated together with the molten iron alloy. In this case, the proportion of boron carbide, which is supplied in the arc wire spraying, 0.5 to 8, preferably 1 to 5 wt.%, So that the proportion of iron alloy from 92 to 99.5 and 95 to 99 wt.%.

Die erfindungsgemäße Beschichtung erfüllt alle Korrosionsanforderungen, die an einen Motorblock aus Aluminium oder dergleichen Leichtmetall gestellt werden, insbesondere auch gegen Salz- und Schwefelkorrosion, vor allem auch bei Kraftstoffen mit erhöhtem Schwefelanteil, z. B. Venezuela-Kraftstoff.The coating of the invention meets all corrosion requirements that are placed on an engine block made of aluminum or the like light metal, in particular against salt and sulfur corrosion, especially in fuels with increased sulfur content, eg. B. Venezuela fuel.

Das Borcarbid wird in der beim Lichtbogendrahtspritzen geschmolzenen Eisenlegierung zumindest teilweise in Eisenborid (FexBx) umgewandelt, wodurch die Beschichtung gehärtet und ihre Verschleißbeständigkeit wesentlich erhöht wird. Durch die Einlagerung von Borcarbid und das Eisenborid in der Beschichtung werden Druckspannungen aufgebaut und damit Enthaftungen verhindert.The boron carbide is at least partially converted to iron boride (Fe x B x ) in the iron alloy molten during arc wire spraying, thereby hardening the coating and substantially increasing its wear resistance. By incorporating boron carbide and the iron boride in the coating compressive stresses are built up and thus prevents delamination.

Als Eisenlegierung hat sich insbesondere eine Legierung folgender Zusammensetzung als vorteilhaft erwiesen:

  • 0,1 bis 0,7 Gew.% C,
  • 10 bis 18 Gew.% Cr,
  • 0,8 bis 2 Gew.% Mo,
  • max. 2 Gew.% Mn,
  • max. 1 Gew.% Si, sowie
  • Fe als Rest und unvermeidbare Verunreinigungen einzeln max. 0,3 Gew.%, insgesamt max. 1,0 Gew.%.
As an iron alloy, in particular an alloy of the following composition has proven advantageous:
  • 0.1 to 0.7% by weight C,
  • 10 to 18% by weight of Cr,
  • 0.8 to 2% by weight of Mo,
  • Max. 2% by weight of Mn,
  • Max. 1 wt.% Si, as well
  • Fe as remainder and unavoidable impurities individually max. 0.3% by weight, in total max. 1.0% by weight.

Das Borcarbid wird vorzugsweise mit einer Teilchengröße von 0,1 bis 10 µm eingesetzt.The boron carbide is preferably used with a particle size of 0.1 to 10 microns.

Das Lichtbogendrahtspritzen(LDS)-Verfahrenwird auch als TWAS (Twin Wire Arc Spraying) bezeichnet.The arc wire spraying (LDS) process is also referred to as TWAS (Twin Wire Arc Spraying).

Dazu werden zwei Drähte, die aus der erfindungsgemäß verwendeten Eisenlegierung bestehen, einem Spritzkopf zugeführt, derart, dass eine Stromübertragung an die Drähte erfolgt, wobei sich die beiden Drähte mit ihrem Ende berühren, wodurch durch einen permanenten Kurzschluss ein Lichtbogen gebildet wird, der die Drähte an ihrem Ende schmelzen lässt. Hinter der Schmelzzone befindet sich eine Düse, aus der Druckluft oder ein inertes Gas, wie Stickstoff, austritt. Dieser Gasstrom zerstäubt die geschmolzene Eisenlegierung und führt sie der zu beschichtenden Oberfläche zu. Dabei wird erfindungsgemäß vorzugsweise ein Schmelzkopf verwendet, der für das Borcarbid eine Zuführung in den Gasstrom stromaufwärts des Lichtbogens aufweist.For this purpose, two wires, which consist of the iron alloy used in the invention, fed to a spray head, such that a current transmission to the wires, wherein the two wires touch with its end, whereby an arc is formed by a permanent short circuit, the wires melting at the end. Behind the melt zone is a nozzle from which compressed air or an inert gas, such as nitrogen, exits. This gas stream atomizes the molten iron alloy and supplies it to the surface to be coated. In this case, according to the invention, preferably a melting head is used, which has a feed into the gas stream upstream of the arc for the boron carbide.

Die Zylinderlaufbahnen eines Verbrennungsmotors werden vor dem Beschichten vorzugsweise mit einem Hochdruckwasserstrahl vorbehandelt. Zur Beschichtung wird der Spritzkopf in einen der Zylinder eingeführt, wobei er während des Spritzens um die Zylinderlängsachse rotiert. Die auf die Zylinderlaufbahn durch thermisches Spritzen aufgebrachte Schicht weist beispielsweise eine Schichtdicke von 0,2 bis 0,6 mm auf. Durch Honen und dergleichen Endbearbeitung wird schließlich beispielsweise eine 0,1 bis 0,2 mm dicke Zylinderlaufbahnbeschichtung erhalten.The cylinder liners of an internal combustion engine are preferably pretreated with a high-pressure water jet before coating. For coating the spray head is inserted into one of the cylinders, wherein it rotates during spraying around the cylinder longitudinal axis. The applied to the cylinder bore by thermal spraying layer, for example, has a layer thickness of 0.2 to 0.6 mm. By honing and the like finish finally, for example, a 0.1 to 0.2 mm thick cylinder liner coating is obtained.

Nachstehend ist eine Vorrichtung zur Durchführung des erfindungsgemäßen Verfahrens anhand der Zeichnung beispielhaft näher erläutert, deren einzige Figur eine Seitenansicht einer Lanze für das LDS-Verfahren mit längsgeschnittenem Spritzkopf zeigt.An apparatus for carrying out the method according to the invention is explained in more detail below by way of example with reference to the drawing, the single FIGURE of which shows a side view of a lance for the LDS method with a longitudinally cut extrusion head.

Danach ist an einer Lanze 1 ein Spritzkopf 2 befestigt. In die Lanze 1 werden, wie durch die Pfeile 3 und 4 dargestellt, zwei Drähte 5, 6 aus der erfindungsgemäßen Eisenlegierung eingeführt, die zu dem Spritzkopf 2 transportiert werden, aus dem sie so austreten, dass sie sich mit ihren Enden 7, 8 berühren. Die Drähte 5, 6 werden mit nicht dargestellten Kontakten mit Strom beaufschlagt, sodass sich an ihren Enden 7, 8 durch einen Kurzschluss ein Lichtbogen und damit eine Schmelzzone 9 bildet.Thereafter, a spray head 2 is attached to a lance 1. In the lance 1, as shown by the arrows 3 and 4, two wires 5, 6 introduced from the iron alloy according to the invention, which are transported to the spray head 2, from which they emerge so that they touch with their ends 7, 8 , The wires 5, 6 are energized with contacts, not shown, so that forms an arc and thus a melting zone 9 at their ends 7, 8 by a short circuit.

Hinter der Schmelzzone 9 weist der Spritzkopf 2 einen Vorsprung 10 auf, der mit einer Düse 11 versehen ist, durch die ein Gasstrom austritt, der, wie durch den Pfeil 12 dargestellt, der Lanze 1 zugeführt und in dem Spritzkopf 2, wie mit 13 gestrichelt dargestellt, zu der Düse 11 strömt.Behind the molten zone 9, the spray head 2 has a projection 10 which is provided with a nozzle 11 through which a gas stream emerges, which, as shown by the arrow 12, the lance 1 and supplied in the spray head 2, as dashed at 13 shown, flows to the nozzle 11.

Dem Vorsprung 10 wird über eine Leitung 14 Borcarbid-Pulver aus einem Vorratsbehälter 15 zugeführt, wodurch das Borcarbid-Pulver durch den Gasstrom 13 aus der Düse 11 in die Schmelzzone 9 geblasen und damit mit der zerstäubten geschmolzenen Eisenlegierung der zu beschichtenden Oberfläche 16 zugeführt wird.The projection 10 is supplied via a line 14 boron carbide powder from a reservoir 15, whereby the Boron carbide powder is blown through the gas stream 13 from the nozzle 11 into the molten zone 9 and thus supplied with the atomized molten iron alloy of the surface 16 to be coated.

Claims (5)

  1. A method of producing a coating by arc wire spraying with an iron alloy and boron carbide, characterised in that the arc wire spraying is performed in a simultaneous supply of 92 to 99.5 wt.% of an iron alloy containing 5 to 25 wt% chromium and 0.5 to 5 wt.% molybdenum and 0.5 to 8 wt.% boron carbide, wherein a wire made of the iron alloy is used and the boron carbide is supplied separately in powder form.
  2. A method according to claim 1, characterised in that the iron alloy contains 10 to 18 wt.% chromium and 0.8 8 to 3 wt.% molybdenum.
  3. A method according to claim 1 or claim 2, characterised in that the iron alloy has the following composition:
    0.1 to 0.7 wt.% carbon,
    10 to 18 wt.% chromium,
    0.8 to 2 wt.% molybdenum,
    up to 2 wt.% manganese,
    up to 1 wt.% silicon and
    remainder iron and unavoidable impurities, up to 0.3 wt.% each, maximum total 1.0 wt.%.
  4. A method according to any of the preceding claims, characterised in that the arc wire spraying is performed with 95 to 99 wt.% of the iron alloy and 1 to 5 wt.% boron carbide.
  5. A method according to any of the preceding claims, characterised in that the boron carbide is used in a particle size of 0.1 to 10 µm.
EP08002244.5A 2007-03-06 2008-02-07 Method for manufacturing a coating Active EP1967601B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102007010698A DE102007010698A1 (en) 2007-03-06 2007-03-06 Process for the preparation of a coating

Publications (3)

Publication Number Publication Date
EP1967601A2 EP1967601A2 (en) 2008-09-10
EP1967601A3 EP1967601A3 (en) 2011-04-27
EP1967601B1 true EP1967601B1 (en) 2013-08-07

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Family Applications (1)

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EP (1) EP1967601B1 (en)
DE (1) DE102007010698A1 (en)

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DE102009019674B4 (en) * 2009-04-30 2016-09-01 Bayerische Motoren Werke Aktiengesellschaft Process for coating a cylinder wall of a crankcase
DE102010021300B4 (en) 2010-05-22 2012-03-22 Daimler Ag Wire-shaped spray material, functional layer that can be produced therewith and method for coating a substrate with a spray material
DE102011015533A1 (en) 2011-03-30 2011-12-29 Daimler Ag Method for operating cylinder liner of cylinder of internal combustion engine for vehicle, involves pretreating cylinder liner by high-pressure water jets and counteracting heating of e cylinder liner and formation of water vapor
DE102011084608A1 (en) 2011-10-17 2013-04-18 Ford-Werke Gmbh Plasma spray process
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DE102011086803A1 (en) 2011-11-22 2013-05-23 Ford Global Technologies, Llc Repair method of a cylinder surface by means of plasma spraying
DE102013200912B4 (en) 2012-02-02 2018-05-30 Ford Global Technologies, Llc crankcase
US9511467B2 (en) 2013-06-10 2016-12-06 Ford Global Technologies, Llc Cylindrical surface profile cutting tool and process
DE102012013020B3 (en) 2012-06-29 2013-05-02 Daimler Ag Function layer comprises an iron based alloy having a martensitic structure, and alloy components indicated in characteristics consisting of nickel equivalent and chromium equivalent
US9079213B2 (en) 2012-06-29 2015-07-14 Ford Global Technologies, Llc Method of determining coating uniformity of a coated surface
DE102012015405B4 (en) * 2012-08-03 2014-07-03 Federal-Mogul Burscheid Gmbh Cylinder liner and method for its production
DE102014003114B3 (en) * 2014-03-11 2014-12-31 Daimler Ag Process for coating a substrate, in which a wire-shaped spray material is melted in an arc and deposited as a layer on the substrate, as well as a wire arc sprayed layer
US9382868B2 (en) 2014-04-14 2016-07-05 Ford Global Technologies, Llc Cylinder bore surface profile and process
DE102015005590A1 (en) * 2015-05-02 2016-03-03 Daimler Ag Thermal sprayed coating
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Publication number Publication date
EP1967601A3 (en) 2011-04-27
EP1967601A2 (en) 2008-09-10
DE102007010698A1 (en) 2008-09-11

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