EP1022351A1 - Plasma sprayed layer on cylinder bores of engine blocks - Google Patents

Plasma sprayed layer on cylinder bores of engine blocks Download PDF

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Publication number
EP1022351A1
EP1022351A1 EP99811122A EP99811122A EP1022351A1 EP 1022351 A1 EP1022351 A1 EP 1022351A1 EP 99811122 A EP99811122 A EP 99811122A EP 99811122 A EP99811122 A EP 99811122A EP 1022351 A1 EP1022351 A1 EP 1022351A1
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Prior art keywords
weight
powder
layer
particle size
gas
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EP99811122A
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German (de)
French (fr)
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EP1022351B2 (en
EP1022351B1 (en
Inventor
Gérard BARBEZAT
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Oerlikon Metco AG
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Sulzer Metco AG
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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
    • C23C4/12—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
    • 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
    • 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 an iron-containing layer for cylinder running surfaces applied by plasma spraying of engine blocks according to claim 1 and a method for manufacturing such layers according to claim 7 or 8.
  • the coating of holes with the help of the plasma spraying process has been going on for a long time known.
  • Various metallic materials can be applied.
  • the layers are passed through Diamond diamonds machined to the final dimension and provided with the desired topography. The workability of the layers and the tribological properties are determined by the microstructure and the physical properties of the corresponding layers significantly influenced.
  • the object of the present invention is the machinability and the tribological properties of plasma-sprayed ferrous layers for cylinder running surfaces of engine blocks to improve.
  • the invention is based on the surprising finding that in a particularly controlled Reaction of the powder used with oxygen during plasma spraying a microstructure can be generated, which is excellent in terms of workability and tribology Has properties. In particular, the coefficient of friction and the Tendency to scuffing ("eating", i.e. the beginning of adhesive wear) drastically reduced.
  • FIGS dependent claims 2 to 6 are shown in FIGS dependent claims 2 to 6 circumscribed.
  • the bound oxygen expediently forms FeO and Fe 3 O 4 crystals with iron.
  • the Fe 2 O 3 content is preferably less than 0.2% by weight.
  • the amount of oxides formed can be further influenced by mixing the air with nitrogen or oxygen. When the air is replaced by pure oxygen, the bound amount of oxygen in the layer is reduced by a factor of about two.
  • the speed of the gas flow in the cylinder bore or the sleeve is expediently 7 to 12 m / s during the coating.
  • 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 expediently in the range from 5 to 25 ⁇ m, 10 to 45 ⁇ m or from 15 to 60 ⁇ m. It can be determined using an optical or electronic microscope, in particular a scanning electron microscope SEM, or using the laser diffraction method MICROTRAC.
  • the best results are obtained if a powder modified by adding a tribological oxide ceramic is used.
  • the oxide ceramic expediently 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 ceramic in the powder used is preferably 5 to 50% by weight.
  • the choice of the optimal 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 hit.
  • the particle size of the powder was between 5 to 25 ⁇ m, and the preparation was carried out by gas atomization.
  • the gas flow velocity during coating of the can was 10 m / s, the amount of air for layer cooling and powder reaction 500 NLPM (corresponding 100 NLPM oxygen). This amount of air was fed through a plasmatron body, e.g. a plasmatron according to EP-B1-0 645 946.
  • Example 1 When using a powder of the same chemical composition as in Example 1, but with a particle size of 10 to 45 ⁇ m, and otherwise under the same boundary conditions as in Example 1, the proportion of bound oxygen in the generated Layers at 2% by weight. The rest of the results of an analysis of the so applied Layer were the same as in example 1.
  • the particle size of the powder was between 10 to 45 ⁇ m, and the preparation was carried out by gas atomization.
  • 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 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). The same effect as in Example 4 was achieved.
  • Fig. 1 shows a diagram from which the reduction in the coefficient of friction depending on the particle size of the powder and the mechanical behavior, especially the adhesive strength of the layer on AlSi substrates, depending on the particle size of the powder emerges.
  • the diagram clearly shows that the coefficient of friction with increasing size of the particles of the coating powder reduced.
  • the adhesive strength of the layer on AlSi substrates decreases as the size of the coating powder particles increases.
  • the particle size to be selected can be in the range of 25-30 m, so that in most cases the adhesive strength is sufficient
  • Layer in the range of 45-50 MPa is to be expected, the coefficient of friction, in comparison with layers according to the prior art, is about 22-25% less.
  • Fig. 2 shows a diagram from which the reduction in the coefficient of friction depending on the amount of bound oxygen in the layer and the mechanical Behavior, specifically the adhesive strength of the layer on AlSi substrates, depending depends on the amount of bound oxygen in the layer. From the On the one hand, the diagram clearly shows that the coefficient of friction increases with increasing The amount of bound oxygen in the layer is reduced. On the other hand, it becomes clear that the adhesive strength of the layer on AlSi substrates decreases when the amount of bound oxygen increases in the layer.
  • a good compromise on what to strive for Amount of bound oxygen in the layer can range from 2-2.5 % By weight, so that in most cases the adhesive strength is sufficient
  • Layer in the range of 40-50 MPa can be expected the coefficient of friction, in comparison with layers according to the prior art, is about 20-25% less. If but, as already explained in connection with FIG. 1, primarily one high adhesive strength of the layer is sought and the reduction in the coefficient of friction is of minor importance, one becomes a coating with a Aim for less than 2% by weight of bound oxygen. On the other hand, if first and foremost an extremely low coefficient of friction is sought and a slightly lower adhesive strength can be accepted, one becomes Select 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)

Abstract

Iron-containing layer applied by plasma spraying contains 1-4 wt.% bound oxygen. An Independent claim is also included for a process for the production of layers comprising injecting an amount of air of 200-1000 NLPM during plasma spraying.

Description

Die Erfindung betrifft eine durch Plasmaspritzen aufgebrachte eisenhaltige Schicht für Zylinderlaufflächen von Motorblöcken nach dem Anspruch 1 sowie ein Verfahren zur Herstellung solcher Schichten nach dem Anspruch 7 oder 8.The invention relates to an iron-containing layer for cylinder running surfaces applied by plasma spraying of engine blocks according to claim 1 and a method for manufacturing such layers according to claim 7 or 8.

Als klassischer Werkstoff für die Zylinderlaufflächen von Aluminium- oder Magnesium-Motorblöcken wird immer noch Gusseisen mit Lamellen- oder Vermikulargraphit, in Form von eingepressten oder eingegossenen Büchsen, verwendet.As a classic material for the cylinder liners of aluminum or magnesium engine blocks cast iron with lamellar or vermicular graphite, in shape of pressed or cast cans.

Durch solche Büchsen wird jedoch zum einen die Grösse und das Gewicht des Motorblocks nachteilig beeinflusst. Zum anderen entsteht eine ungünstige Verbindung zwischen den Gusseisenbüchsen und dem aus Leichtmetall bestehenden Motorblock. Als Alternative werden auch galvanische Schichten eingesetzt. Deren Aufbringen ist jedoch kostenintensiv und zudem sind sie gegenüber Schwefel- und Ameisensäure korrosionsanfällig.Such bushings, on the one hand, increase the size and weight of the engine block adversely affected. On the other hand, there is an unfavorable connection between the cast iron cans and the engine block made of light metal. As alternative galvanic layers are also used. However, applying them is costly and they are also susceptible to corrosion from sulfuric and formic acid.

Weiter ist das Beschichten von Bohrungen mit Hilfe des Plasmaspritzverfahrens seit langem bekannt. Dabei können verschiedene metallische Werkstoffe aufgebracht werden. Nach dem Beschichten mittels des Plasmaspritzverfahrens werden die Schichten durch Diamanthonen auf das Endmass bearbeitet und mit der gewünschten Topographie versehen. Die Bearbeitbarkeit der Schichten und die tribologischen Eigenschaften werden durch das Mikrogefüge und die physikalischen Eigenschaften der entsprechenden Schichten massgebend beeinflusst.Furthermore, the coating of holes with the help of the plasma spraying process has been going on for a long time known. Various metallic materials can be applied. After coating by means of the plasma spraying process, the layers are passed through Diamond diamonds machined to the final dimension and provided with the desired topography. The workability of the layers and the tribological properties are determined by the microstructure and the physical properties of the corresponding layers significantly influenced.

Aufgabe der vorliegenden Erfindung ist es, die Zerspanbarkeit und die tribologischen Eigenschaften von durch Plasmaspritzen aufgebrachten eisenhaltigen Schichten für Zylinderlaufflächen von Motorblöcken zu verbessern.The object of the present invention is the machinability and the tribological properties of plasma-sprayed ferrous layers for cylinder running surfaces of engine blocks to improve.

Diese Aufgabe wird durch die im Kennzeichen des Anspruchs 1 umschriebene Schicht bzw. durch das im Kennzeichen des Anspruchs 7 oder 8 umschriebene Verfahren gelöst. This object is achieved by the layer described in the characterizing part of claim 1 or solved by the method described in the characterizing part of claim 7 or 8.

Die Erfindung beruht auf der überraschenden Feststellung, dass bei einer besonders kontrollierten Reaktion des eingesetzten Pulvers mit Sauerstoff beim Plasmaspritzen ein Mikrogefüge erzeugt werden kann, welches bezüglich Bearbeitbarkeit und Tribologie hervorragende Eigenschaften aufweist. Insbesondere werden die Reibungskoeffizienten und die Neigung zum Scuffing ("Fressen", d. h. dem Beginn des adhäsiven Verschleisses) drastisch verringert.The invention is based on the surprising finding that in a particularly controlled Reaction of the powder used with oxygen during plasma spraying a microstructure can be generated, which is excellent in terms of workability and tribology Has properties. In particular, the coefficient of friction and the Tendency to scuffing ("eating", i.e. the beginning of adhesive wear) drastically reduced.

Die erfindungsgemässen durch Plasmaspritzen aufgebrachten eisenhaltigen Schichten für Zylinderlaufflächen von Motorblöcken sind dadurch gekennzeichnet, dass der Gehalt an gebundenem Sauerstoff 1 bis 4 Gewichts-% beträgt. Für die Beschichtung kommen insbesondere in Frage:

  • die Zylinderbohrungen von Motorblöcken aus Aluminium- oder Magnesium- Legierungen oder aus Gusseisen; oder
  • die innere Zylinderwand von in Aluminium- oder Magnesium-Motorblöcke eingesetzten Gusseisenbüchsen.
The iron-containing layers according to the invention applied by plasma spraying for cylinder running surfaces of engine blocks are characterized in that the bound oxygen content is 1 to 4% by weight. The following are particularly suitable for the coating:
  • the cylinder bores of engine blocks made of aluminum or magnesium alloys or cast iron; or
  • the inner cylinder wall of cast iron liners used in aluminum or magnesium engine blocks.

Bevorzugte Ausführungen der durch Plasmaspritzen aufgebrachten Schichten sind in den abhängigen Ansprüchen 2 bis 6 umschrieben.Preferred versions of the layers applied by plasma spraying are shown in FIGS dependent claims 2 to 6 circumscribed.

Zweckmässigerweise bildet der gebundene Sauerstoff mit Eisen FeO- und Fe3O4-Kristalle. Vorzugsweise beträgt der Gehalt an Fe2O3 weniger als 0,2 Gewichts-%. Die Menge der gebildeten Oxyde kann durch Mischen der Luft mit Stickstoff oder Sauerstoff weiter beeinflusst werden. Beim Ersetzen der Luft durch reinen Sauerstoff wird der gebundene Anteil an Sauerstoff in der Schicht um einen Faktor von etwa zwei reduziert.The bound oxygen expediently forms FeO and Fe 3 O 4 crystals with iron. The Fe 2 O 3 content is preferably less than 0.2% by weight. The amount of oxides formed can be further influenced by mixing the air with nitrogen or oxygen. When the air is replaced by pure oxygen, the bound amount of oxygen in the layer is reduced by a factor of about two.

Das erfindungsgemässe Verfahren zur Herstellung der erfindungsgemässen Schichten ist dadurch gekennzeichnet, dass während des Plasmaspritzens eine Luftmenge von 200 bis 1000 NLPM (Normal-Liter pro Minute, d.h. bei 1 bar [= 105 Pa] und 20°C) oder eine Gasmenge mit 40 bis 200 NLPM Sauerstoff zugegeben wird. Zweckmässigerweise beträgt die Geschwindigkeit der Gasströmung in der Zylinderbohrung oder der Büchse während des Beschichtens 7 bis 12 m/s. The method according to the invention for producing the layers according to the invention is characterized in that during the plasma spraying an air volume of 200 to 1000 NLPM (normal liters per minute, ie at 1 bar [= 10 5 Pa] and 20 ° C.) or a gas volume of 40 until 200 NLPM oxygen is added. The speed of the gas flow in the cylinder bore or the sleeve is expediently 7 to 12 m / s during the coating.

Bevorzugte Verfahren werden in den Ansprüchen 9 bis 20 beansprucht.Preferred methods are claimed in claims 9 to 20.

Zweckmässigerweise wird für die Beschichtung ein gasverdüstes Pulver folgender chemischer Zusammensetzung eingesetzt:

  • C = 0,4 bis 1,5 Gewichts-%
  • Cr = 0,2 bis 2,5 Gewichts-%
  • Mn = 0,2 bis 3 Gewichts-%
  • S = 0,01 bis 0,2 Gewichts-%
  • P = 0,01 bis 0,1 Gewichts-%.
  • Fe = Differenz auf 100 Gewichts-%
    • A gas-atomized powder of the following chemical composition is expediently used for the coating:
  • C = 0.4 to 1.5% by weight
  • Cr = 0.2 to 2.5% by weight
  • Mn = 0.2 to 3% by weight
  • S = 0.01 to 0.2% by weight
  • P = 0.01 to 0.1% by weight.
  • Fe = difference to 100% by weight

    • Alternativ kann für die Beschichtung ein gasverdüstes Pulver folgender chemischer Zusammensetzung eingesetzt werden:

  • C = 0,1 bis 0,8 Gewichts-%
  • Cr = 11 bis 18 Gewichts-%
  • Mn = 0,1 bis 1,5 Gewichts-%
  • Mo = 0,1 bis 5 Gewichts-%
  • S = 0,01 bis 0,2 Gewichts-%
  • P = 0,01 bis 0,1 Gewichts-%.
  • Fe = Differenz auf 100 Gewichts-%
    • Alternatively, a gas-atomized powder of the following chemical composition can be used for the coating:
  • C = 0.1 to 0.8% by weight
  • Cr = 11 to 18% by weight
  • Mn = 0.1 to 1.5% by weight
  • Mo = 0.1 to 5% by weight
  • S = 0.01 to 0.2% by weight
  • P = 0.01 to 0.1% by weight.
  • Fe = difference to 100% by weight

    • Das Volumen von FeO und Fe3O4 kann durch Auswahl der Partikelgrössenverteilung beeinflusst werden. Zweckmässigerweise liegt die Partikelgrösse des Pulvers im Bereich von 5 bis 25 µm, 10 bis 45 µm oder von 15 bis 60 µm. Sie kann mittels eines optischen oder elektronischen Mikroskops, insbesondere eines Rasterelektronenmikroskop REM, oder nach der Laserbeugungsmethode MICROTRAC bestimmt werden.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 expediently in the range from 5 to 25 μm, 10 to 45 μm or from 15 to 60 μm. It can be determined using an optical or electronic microscope, in particular a scanning electron microscope SEM, or using the laser diffraction method MICROTRAC.

    Zweckmässigerweise wird ein durch Gasverdüsung mit Argon oder Stickstoff erhaltenes Pulver eingesetzt. Expediently, one obtained by gas atomization with argon or nitrogen Powder used.

    Beste Resultate werden erhalten, wenn ein durch Zugabe einer tribologischen Oxydkeramik modifiziertes Pulver eingesetzt wird. Zweckmässigerweise besteht die Oxydkeramik aus TiO2 oder Al2O3TiO2- und/oder Al2O3ZrO2-Legierungssystemen. Der Anteil an Oxydkeramik im eingesetzten Pulver beträgt vorzugsweise 5 bis 50 Gewichts-%.The best results are obtained if a powder modified by adding a tribological oxide ceramic is used. The oxide ceramic expediently 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 ceramic in the powder used is preferably 5 to 50% by weight.

    Die Wahl der optimalen Grösse der Pulverpartikel wird unter Berücksichtigung der tribologischen Eigenschaften der erzeugten Schichten und des mechanischen Verhaltens des Systemschichtsubstrates getroffen.The choice of the optimal 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 hit.

    In folgenden werden Ausführungsbeispiele der erfindungsgemässen Schicht anhand von Beispielen näher erläutert. In den beiliegenden Zeichnungen zeigen:

    Fig. 1
    ein Diagramm, aus dem die Verminderung des Reibungskoeffizienten in Abhängigkeit von der Partikelgrösse des Pulvers und das mechanische Verhalten (Haftfestigkeit) der Schicht auf AlSi-Substraten in Abhängigkeit von der Partikelgrösse des Pulvers hervorgeht; und
    Fig. 2
    ein Diagramm, aus dem die Verminderung des Reibungskoeffizienten in Abhängigkeit von der Menge des gebundenen Sauerstoffs im Pulver und das mechanische Verhalten (Haftfestigkeit) der Schicht auf AlSi-Substraten in Abhängigkeit von der Menge des gebundenen Sauerstoffs im Pulver hervorgeht.
    Exemplary embodiments of the layer according to the invention are explained in more detail below with the aid of examples. In the accompanying drawings:
    Fig. 1
    a diagram showing the reduction in the coefficient of friction as a function of the particle size of the powder and the mechanical behavior (adhesive strength) of the layer on AlSi substrates as a function of the particle size of the powder; and
    Fig. 2
    a diagram showing the reduction in the coefficient of friction depending on the amount of bound oxygen in the powder and the mechanical behavior (adhesive strength) of the layer on AlSi substrates depending on the amount of bound oxygen in the powder.

    Beispiel 1example 1

    Ein Pulver der nachstehenden Zusammensetzung wurde mit Hilfe eines Plasmatrons unter folgenden spezifischen Bedingungen auf die Lauffläche einer Zylinderbüchse aufgebracht:

    Pulver:
    C = 1,1 Gewichts-%
    Cr = 1,5 Gewichts-%
    Mn = 1,5 Gewichts-%
    Fe = Differenz auf 100 Gewichts-%.
    Gegebenenfalls kann das Pulver auch geringe Mengen (0.01 - 0.2 Gew.-%) von S und P enthalten.
    A powder of the following composition was applied to the tread of a cylinder liner using a plasma cartridge under the following specific conditions:
    Powder:
    C = 1.1% by weight
    Cr = 1.5% by weight
    Mn = 1.5% by weight
    Fe = difference to 100% by weight.
    If necessary, the powder may also contain small amounts (0.01-0.2% by weight) of S and P.

    Die Partikelgrösse des Pulvers betrug zwischen 5 bis 25 µm, und die Herstellung erfolgte durch Gasverdüsen.The particle size of the powder was between 5 to 25 μm, and the preparation was carried out by gas atomization.

    Die Geschwindigkeit der Gasströmung während des Beschichtens der Büchse betrug 10 m/s, die Luftmenge für die Schichtkühlung und Pulverreaktion 500 NLPM (entsprechend 100 NLPM Sauerstoff). Diese Luftmenge wurde durch einen Plasmatronkörper zugeführt, z.B. ein Plasmatron gemäss EP-B1-0 645 946.The gas flow velocity during coating of the can was 10 m / s, the amount of air for layer cooling and powder reaction 500 NLPM (corresponding 100 NLPM oxygen). This amount of air was fed through a plasmatron body, e.g. a plasmatron according to EP-B1-0 645 946.

    Die Ergebnisse der durchgeführten Untersuchungen zeigen, dass der Sauerstoffgehalt in der erzeugten Schicht bei 3 Gewichts-% liegt. Der Sauerstoff ist gemäss Untersuchungen mittels Röntgenfeinstrukturanalyse unter den stöchiometrischen Formeln FeO und Fe3O4 gebunden. Durch diese Untersuchungen wurde auch festgestellt, dass die Bildung von Fe203 unterhalb der Nachweisgrenze liegt.The results of the tests carried out show that the oxygen content in the layer produced is 3% by weight. According to investigations by means of X-ray fine structure analysis, the oxygen is bound under the stoichiometric formulas FeO and Fe 3 O 4 . These investigations also found that the formation of Fe203 is below the detection limit.

    Die nach der anschliessenden Bearbeitung der erzeugten Schichten durch Diamanthonen durchgeführten Motorversuche haben gezeigt, dass die Reibungskoeffizienten zwischen Kolbenring und Zylinderwandung im Vergleich zu klassischen Gusseisenbüchsen mit Lamellengraphit deutlich reduziert sind.That after the subsequent processing of the layers created by diamond honing engine tests have shown that the coefficient of friction between Piston ring and cylinder wall compared to classic cast iron liners with lamellar graphite are significantly reduced.

    Beispiel 2Example 2

    Bei Verwendung eines Pulvers gleicher chemischer Zusammensetzung wie in Beispiel 1, jedoch mit einer Partikelgrösse von 10 bis 45 µm, und im übrigen unter denselben Randbedingungen wie im Beispiel 1, liegt der Anteil an gebundenem Sauerstoff in den erzeugten Schichten bei 2 Gewichts-%. Die restlichen Ergebnisse einer Analyse der so aufgebrachten Schicht waren gleich wie im Beispiel 1. When using a powder of the same chemical composition as in Example 1, but with a particle size of 10 to 45 µm, and otherwise under the same boundary conditions as in Example 1, the proportion of bound oxygen in the generated Layers at 2% by weight. The rest of the results of an analysis of the so applied Layer were the same as in example 1.

    Die durchgeführten Untersuchungen zeigen im Motortest ähnlich günstige Ergebnisse, wobei die Reduktion der Reibungskoeffizienten im Zusammenhang mit dem Anteil an gebundenem Sauerstoff steht.The tests carried out show similarly favorable results in the engine test, the reduction in the coefficient of friction in connection with the proportion of bound Oxygen stands.

    Beispiel 3Example 3

    Für Motoren, die durch Verbrennung von schwefelhaltigen Kraftstoffen oder von Methanol, bei Temperaturen unter dem Taupunkt bei den herrschenden Bedingungen, korrosionsgefährdet sind, wurde die Beschichtung unter den Bedingungen gemäss Beispiel 1 mit folgendem Pulver vorgenommen:

    Pulver:
    C = 0,4 Gewichts-%
    Cr = 13 Gewichts-%
    Mn = 1,5 Gewichts-%
    Mo = 2 Gewichts-%
    Fe = Differenz auf 100 Gewichts-%
    Gegebenenfalls kann das Pulver auch geringe Mengen (0.01 - 0.2 Gew.-%) von S und P enthalten.
    For engines which are at risk of corrosion due to the combustion of sulfur-containing fuels or methanol at temperatures below the dew point under the prevailing conditions, the coating was carried out under the conditions according to Example 1 using the following powder:
    Powder:
    C = 0.4% by weight
    Cr = 13% by weight
    Mn = 1.5% by weight
    Mo = 2% by weight
    Fe = difference to 100% by weight
    If necessary, the powder may also contain small amounts (0.01-0.2% by weight) of S and P.

    Die Partikelgrösse des Pulvers betrug zwischen 10 bis 45 µm, und die Herstellung erfolgte durch Gasverdüsen.The particle size of the powder was between 10 to 45 μm, and the preparation was carried out by gas atomization.

    Die Versuche, die mit einem mit einer derartigen Zylinderlauffläche versehenen Verbrennungsmotor durchgeführt wurden, haben im wesentlichen zu denselben Ergebnissen wie in Beispielen 1 und 2 erwähnt geführt.The tests with an internal combustion engine provided with such a cylinder tread have substantially the same results as mentioned in Examples 1 and 2.

    Beispiel 4Example 4

    Dem Pulver gemäss Beispiel 2 wurde eine Menge von 30 Gewichts-% eines legierten Keramikpulvers, bestehend aus 60 Gewichts-% Al2O3 und 40 Gewichts-% TiO2, zugegeben. Die mittels dieser Pulvermischung erzeugten Schichten sind durch die Einlagerung der Keramikpartikel (Partikelgrösse 5 bis 22 µm) mechanisch verstärkt. An amount of 30% by weight of an alloyed ceramic powder consisting of 60% by weight Al 2 O 3 and 40% by weight TiO 2 was added to the powder according to Example 2. The layers produced by means of this powder mixture are mechanically reinforced by the incorporation of the ceramic particles (particle size 5 to 22 µm).

    Beispiel 5Example 5

    Analog zu Beispiel 4 wurden 30 Gewichts-% eines legierten Keramikpulvers, bestehend aus 80 Gewichts-% Al2O3 und 20 Gewichts-% ZrO2, zugegeben. Die mittels dieser Pulvermischung erzeugten Schichten sind durch die Einlagerung der Keramikpartikel (Partikelgrösse 5 bis 22 µm) mechanisch verstärkt. Dabei wurde derselbe Effekt wie in Beispiel 4 erzielt.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 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 µm). The same effect as in Example 4 was achieved.

    Fig. 1 zeigt ein Diagramm, aus dem die Verminderung des Reibungskoeffizienten in Abhängigkeit von der Partikelgrösse des Pulvers und das mechanische Verhalten, namentlich die Haftfestigkeit der Schicht auf AlSi-Substraten, in Abhängigkeit von der Partikelgrösse des Pulvers hervorgeht. Aus dem Diagramm ist einerseits klar ersichtlich, dass sich der Reibungskoeffizient mit zunehmender Grösse der Partikel des Beschichtungspulvers vermindert. Andererseits wird deutlich, dass die Haftfestigkeit der Schicht auf AlSi-Substraten abnimmt, wenn die Grösse der Partikel des Beschichtungspulvers zunimmt. Ein guter Kompromiss bezüglich der zu wählenden Partikelgrösse kann im Bereich von 25-30 m liegen, sodass mit einer in den meisten Fällenden ausreichenden Haftfestigkeit der Schicht im Bereich von 45-50 MPa zu rechnen ist, wobei der Reibungskoeffizient, im Vergleich mit Schichten gemäss dem Stand der Technik, um ca. 22-25% geringer ist. Wenn aber in erster Linie eine ausgesprochen hohe Haftfestigkeit der Schicht angestrebt wird und die Verminderung des Reibungskoeffizienten eher von untergeordneter Bedeutung ist, wird man ein Beschichtungspulver mit einer Partikelgrösse von weniger als 25 um wählen. Andererseits, wenn in erster Linie ein ausgesprochen geringer Reibungskoeffizient angestrebt wird und eine etwas geringere Haftfestigkeit in Kauf genommen werden kann, wird man ein Beschichtungspulver mit einer Partikelgrösse von mehr als 35 m wählen.Fig. 1 shows a diagram from which the reduction in the coefficient of friction depending on the particle size of the powder and the mechanical behavior, especially the adhesive strength of the layer on AlSi substrates, depending on the particle size of the powder emerges. On the one hand, the diagram clearly shows that the coefficient of friction with increasing size of the particles of the coating powder reduced. On the other hand, it is clear that the adhesive strength of the layer on AlSi substrates decreases as the size of the coating powder particles increases. On good compromise regarding the particle size to be selected can be in the range of 25-30 m, so that in most cases the adhesive strength is sufficient Layer in the range of 45-50 MPa is to be expected, the coefficient of friction, in comparison with layers according to the prior art, is about 22-25% less. If but first and foremost, an extremely high adhesive strength of the layer is sought and the reduction in the coefficient of friction is of minor importance will choose a coating powder with a particle size of less than 25 microns. On the other hand, if the goal is to achieve an extremely low coefficient of friction and a slightly lower adhesive strength can be accepted to choose a coating powder with a particle size of more than 35 m.

    Fig. 2 zeigt ein Diagramm, aus dem die Verminderung des Reibungskoeffizienten in Abhängigkeit von der Menge des gebundenen Sauerstoffs in der Schicht und das mechanische Verhalten, namentlich die Haftfestigkeit der Schicht auf AlSi-Substraten, in Abhängigkeit von der Menge des gebundenen Sauerstoffs in der Schicht hervorgeht. Aus dem Diagramm ist einerseits klar ersichtlich, dass sich der Reibungskoeffizient mit zunehmender Menge des gebundenen Sauerstoffs in der Schicht vermindert. Andererseits wird deutlich, dass die Haftfestigkeit der Schicht auf AlSi-Substraten abnimmt, wenn die Menge des gebundenen Sauerstoffs in der Schicht zunimmt. Ein guter Kompromiss bezüglich der anzustrebenden Menge an gebundenem Sauerstoff in der Schicht kann im Bereich von 2-2.5 Gew.-% liegen, sodass mit einer in den meisten Fällen ausreichenden Haftfestigkeit der Schicht im Bereich von 40-50 MPa zu rechnen ist, wobei der Reibungskoeffizient, im Vergleich mit Schichten gemäss dem Stand der Technik, um ca. 20-25% geringer ist. Wenn aber, wie bereits im Zusammenhang mit Fig. 1 erläutert, in erster Linie eine ausgesprochen hohe Haftfestigkeit der Schicht angestrebt wird und die Verminderung des Reibungskoeffizienten eher von untergeordneter Bedeutung ist, wird man eine Beschichtung mit einem Anteil an gebundenem Sauerstoff von weniger als 2 Gew.-% anstreben. Andererseits, wenn in erster Linie ein ausgesprochen geringer Reibungskoeffizient angestrebt wird und eine etwas geringere Haftfestigkeit in Kauf genommen werden kann, wird man eine Schicht mit einem Anteil an gebundenem Sauerstoff von mehr als 2.5 Gew.-% wählen.Fig. 2 shows a diagram from which the reduction in the coefficient of friction depending on the amount of bound oxygen in the layer and the mechanical Behavior, specifically the adhesive strength of the layer on AlSi substrates, depending depends on the amount of bound oxygen in the layer. From the On the one hand, the diagram clearly shows that the coefficient of friction increases with increasing The amount of bound oxygen in the layer is reduced. On the other hand, it becomes clear that the adhesive strength of the layer on AlSi substrates decreases when the amount of bound oxygen increases in the layer. A good compromise on what to strive for Amount of bound oxygen in the layer can range from 2-2.5 % By weight, so that in most cases the adhesive strength is sufficient Layer in the range of 40-50 MPa can be expected, the coefficient of friction, in comparison with layers according to the prior art, is about 20-25% less. If but, as already explained in connection with FIG. 1, primarily one high adhesive strength of the layer is sought and the reduction in the coefficient of friction is of minor importance, one becomes a coating with a Aim for less than 2% by weight of bound oxygen. On the other hand, if first and foremost an extremely low coefficient of friction is sought and a slightly lower adhesive strength can be accepted, one becomes Select a layer with a bound oxygen content of more than 2.5% by weight.

    Claims (21)

    Durch Plasmaspritzen aufgebrachte eisenhaltige Schicht für Zylinderlaufflächen von Motorblöcken, dadurch gekennzeichnet, dass der Gehalt an gebundenem Sauerstoff in der Schicht 1 bis 4 Gewichts-% beträgt.Ferrous layer for cylinder running surfaces of Engine blocks, characterized in that the bound oxygen content is 1 to 4% by weight in the layer. Schicht nach Anspruch 1, dadurch gekennzeichnet, dass der gebundene Sauerstoff mit Eisen FeO- und Fe3O4-Kristalle bildet.Layer according to claim 1, characterized in that the bound oxygen forms iron with FeO and Fe 3 O 4 crystals. Schicht nach Anspruch 2, dadurch gekennzeichnet, dass der Gehalt an Fe2O3 weniger als 0,2 Gewichts-% beträgt.Layer according to claim 2, characterized in that the Fe 2 O 3 content is less than 0.2% by weight. Schicht nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Substrat für die aufzutragende Schicht der aus einer Aluminium- oder Magnesiumlegierung oder aus Gusseisen bestehende Motorblock selbst ist.Layer according to one of claims 1 to 3, characterized in that the substrate for the layer to be applied from an aluminum or magnesium alloy or engine block made of cast iron itself. Schicht nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Substrat für die aufzutragenden Schicht eine in einen Motorblock aus einer Aluminium- oder Magnesiumlegierung eingesetzte Büchse aus Gusseisen ist.Layer according to one of claims 1 to 3, characterized in that the substrate for the layer to be applied into an engine block made of an aluminum or magnesium alloy bushing made of cast iron. Schicht nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass das Gusseisen mit Lamellen- oder Vermikulargraphit versetzt ist.Layer according to claim 4 or 5, characterized in that the cast iron with Lamellar or vermicular graphite is offset. Verfahren zur Herstellung von Schichten nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass während des Plasmaspritzens eine Luftmenge von 200 bis 1000 NLPM zugegeben wird.Process for the production of layers according to one of Claims 1 to 6, characterized characterized that during the plasma spraying an air volume of 200 to 1000 NLPM is added. Verfahren zur Herstellung von Schichten nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass während des Plasmaspritzens eine Gasmenge mit 40 bis 200 NLPM Sauerstoff zugegeben wird. Process for the production of layers according to one of Claims 1 to 6, characterized characterized in that during the plasma spraying a gas amount of 40 to 200 NLPM oxygen is added. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass während des Plasmaspritzens reiner Sauerstoff zugegeben wird.A method according to claim 8, characterized in that during the plasma spraying pure oxygen is added. Verfahren nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass die Geschwindigkeit der Gasströmung innerhalb der zu beschichtenden Zylinderbohrung bzw. Büchse während des Beschichtens 7 bis 12 m/s beträgt.Method according to one of claims 7 to 9, characterized in that the speed the gas flow within the cylinder bore to be coated or sleeve during coating is 7 to 12 m / s. Verfahren nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass für die Beschichtung ein gasverdüstes Pulver folgender chemischen Zusammensetzung eingesetzt wird: C = 0,4 bis 1,5 Gewichts-% Cr = 0,2 bis 2,5 Gewichts-% Mn = 0,2 bis 3 Gewichts-% Fe = Differenz auf 100 Gewichts-%. Method according to one of claims 7 to 10, characterized in that a gas-atomized powder of the following chemical composition is used for the coating: C = 0.4 to 1.5% by weight Cr = 0.2 to 2.5% by weight Mn = 0.2 to 3% by weight Fe = difference to 100% by weight. Verfahren nach einem der Ansprüche 7-10, dadurch gekennzeichnet, dass für die Beschichtung ein gasverdüstes Pulver folgender chemischen Zusammensetzung eingesetzt wird: C = 0,1 bis 0,8 Gewichts-% Cr = 11 bis 18 Gewichts-% Mn = 0,1 bis 1,5 Gewichts-% Mo = 0,1 bis 5 Gewichts-% Fe = Differenz auf 100 Gewichts-%. Method according to one of claims 7-10, characterized in that a gas-atomized powder of the following chemical composition is used for the coating: C = 0.1 to 0.8% by weight Cr = 11 to 18% by weight Mn = 0.1 to 1.5% by weight Mo = 0.1 to 5% by weight Fe = difference to 100% by weight. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass das Pulver zusätzlich enthält: S = 0,01 bis 0,2 Gewichts-% P = 0,01 bis 0,1 Gewichts-%. A method according to claim 11 or 12, characterized in that the powder additionally contains: S = 0.01 to 0.2% by weight P = 0.01 to 0.1% by weight. Verfahren nach einem der Ansprüche 7 bis 13, dadurch gekennzeichnet, dass das Volumen von FeO und Fe3O4 durch Auswahl der Partikelgrössenverteilung beeinflusst wird. Method according to one of claims 7 to 13, characterized in that the volume of FeO and Fe 3 O 4 is influenced by selection of the particle size distribution. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Partikelgrösse des Pulvers im Bereich von 5 bis 25 µm liegt.A method according to claim 14, characterized in that the particle size of the Powder is in the range of 5 to 25 microns. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Partikelgrösse des Pulvers im Bereich von 10 bis 45 µm liegt.A method according to claim 14, characterized in that the particle size of the Powder is in the range of 10 to 45 microns. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Partikelgrösse des Pulvers im Bereich von 15 bis 60 µm liegt.A method according to claim 14, characterized in that the particle size of the Powder is in the range of 15 to 60 microns. Verfahren nach einem oder mehreren der Ansprüche 11 bis 17, dadurch gekennzeichnet, dass ein durch Gasverdüsung mit Argon oder Stickstoff erhaltenes Pulver eingesetzt wird.Method according to one or more of claims 11 to 17, characterized in that that a powder obtained by gas atomization with argon or nitrogen is used. Verfahren nach einem oder mehreren der Ansprüche 11 bis 18, dadurch gekennzeichnet, dass ein durch Zugabe einer tribologischen Oxydkeramik modifiziertes Pulver eingesetzt wird.Method according to one or more of claims 11 to 18, characterized in that that a powder modified by adding a tribological oxide ceramic is used. Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass eine Oxydkeramik, welche aus TiO2 oder aus Al2O3TiO2- und/oder Al2O3ZrO2-Legierungssystemen besteht, eingesetzt wird.Method according to claim 19, characterized in that an oxide ceramic consisting of TiO 2 or of Al 2 O 3 TiO 2 and / or Al 2 O 3 ZrO 2 alloy systems is used. Verfahren nach Anspruch 19 oder 20, dadurch gekennzeichnet, dass der Anteil an Oxydkeramik im eingesetzten Pulver 5 bis 50 Gewichts-% beträgt.A method according to claim 19 or 20, characterized in that the proportion of Oxide ceramics in the powder used is 5 to 50% by weight.
    EP99811122A 1999-01-19 1999-12-08 Plasma sprayed layer on cylinder bores of engine blocks Expired - Lifetime EP1022351B2 (en)

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    Cited By (16)

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    EP1113086A1 (en) * 1999-12-27 2001-07-04 Volkswagen Aktiengesellschaft Steel material for plasma deposition
    US6578539B2 (en) 2000-06-14 2003-06-17 Sulzer Metco Ag Surface layer forming a cylinder barrel surface, a spraying powder suitable therefor and a method of creating such a surface layer
    EP1340834A2 (en) * 2002-02-27 2003-09-03 Sulzer Metco AG Coated running surfaces of combustion-engine cylinders and process of its manufacture
    US6701882B2 (en) 2002-02-27 2004-03-09 Sulzer Metco Ag Surface layer for the working surface of the cylinders of a combustion engine and process of applying the surface layer
    EP1340834A3 (en) * 2002-02-27 2004-03-31 Sulzer Metco AG Coated running surfaces of combustion-engine cylinders and process of its manufacture
    EP1757710A1 (en) 2005-08-23 2007-02-28 Sulzer Metco Coatings GmbH Workpiece with a thermal sprayed coating layer
    DE102005040015B3 (en) * 2005-08-23 2007-04-12 Brückner Maschinenbau GmbH Roller and method for its production
    WO2008031468A3 (en) * 2006-09-11 2008-07-10 Federal Mogul Burscheid Gmbh Wet cylinder sleeve having a cavitation-resistant surface
    WO2008031468A2 (en) * 2006-09-11 2008-03-20 Federal-Mogul Burscheid Gmbh Wet cylinder sleeve having a cavitation-resistant surface
    JP2012522896A (en) * 2009-04-07 2012-09-27 フェデラル−モーグル ブルシェイド ゲーエムベーハー Sliding element with adjustable characteristics
    WO2011147526A1 (en) * 2010-05-22 2011-12-01 Daimler Ag Wire-like spray material, functional layer which can be produced therewith and process for coating a substrate with a spray material
    US9487660B2 (en) 2010-05-22 2016-11-08 Daimler Ag Wire-like spray material, functional layer which can be produced therewith and process for coating a substrate with a spray material
    FR2974610A1 (en) * 2011-04-26 2012-11-02 Peugeot Citroen Automobiles Sa Method for producing surfaces of combustion chamber of engine block of vehicle, involves mechanically applying aqueous solution of stable salt on surface of barrels for enhancing chemical bonding between iron and aluminum alloy
    DE102012112394A1 (en) * 2012-12-17 2014-06-18 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Method for manufacturing coated component used in seat of motor car, involves coating region of to-be-coated surface of coated component made of magnesium material by performing thermal spraying process
    EP2829713A1 (en) 2013-07-26 2015-01-28 Sulzer Metco AG Workpiece with a recess for holding a piston
    US9556819B2 (en) 2013-07-26 2017-01-31 Oerlikon Metco Ag, Wohlen Workpiece having a cut-out for receiving a piston

    Also Published As

    Publication number Publication date
    JP4644687B2 (en) 2011-03-02
    DE59914394D1 (en) 2007-08-09
    EP1022351B2 (en) 2009-02-25
    EP1507020A3 (en) 2005-04-20
    KR100593342B1 (en) 2006-06-26
    CA2296155E (en) 2000-07-19
    KR20000071238A (en) 2000-11-25
    US6548195B1 (en) 2003-04-15
    US20020051851A1 (en) 2002-05-02
    PT1022351E (en) 2004-10-29
    ES2288232T3 (en) 2008-01-01
    US6572931B2 (en) 2003-06-03
    JP2000212717A (en) 2000-08-02
    ES2221343T5 (en) 2009-06-12
    EP1507020B1 (en) 2007-06-27
    CA2296155C (en) 2004-09-14
    CA2296155A1 (en) 2000-07-19
    JP2007191795A (en) 2007-08-02
    EP1022351B1 (en) 2004-05-19
    DE59909522D1 (en) 2004-06-24
    ES2221343T3 (en) 2004-12-16
    ATE365814T1 (en) 2007-07-15
    EP1507020A2 (en) 2005-02-16
    JP3967511B2 (en) 2007-08-29
    PT1507020E (en) 2007-07-13
    ATE267275T1 (en) 2004-06-15

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