EP1022351A1 - Plasma sprayed layer on cylinder bores of engine blocks - Google Patents
Plasma sprayed layer on cylinder bores of engine blocks Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- powder
- layer
- particle size
- gas
- 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.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000007750 plasma spraying Methods 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 9
- 229910001018 Cast iron Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011224 oxide ceramic Substances 0.000 claims description 6
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000009689 gas atomisation Methods 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004157 plasmatron Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/14—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.
Landscapes
- 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
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
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
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 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
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:
Alternativ kann für die Beschichtung ein gasverdüstes Pulver folgender chemischer Zusammensetzung
eingesetzt werden:
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.
- 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.
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.
- 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.
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.
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.
- 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.
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 (
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 (
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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04011394A EP1507020B1 (en) | 1999-01-19 | 1999-12-08 | Plasma sprayed layer on cylinder bores of engine blocks |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH9199 | 1999-01-19 | ||
CH9199 | 1999-01-19 | ||
CH24599 | 1999-02-09 | ||
CH24599 | 1999-02-09 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04011394A Division EP1507020B1 (en) | 1999-01-19 | 1999-12-08 | Plasma sprayed layer on cylinder bores of engine blocks |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1022351A1 true EP1022351A1 (en) | 2000-07-26 |
EP1022351B1 EP1022351B1 (en) | 2004-05-19 |
EP1022351B2 EP1022351B2 (en) | 2009-02-25 |
Family
ID=25683486
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04011394A Expired - Lifetime EP1507020B1 (en) | 1999-01-19 | 1999-12-08 | Plasma sprayed layer on cylinder bores of engine blocks |
EP99811122A Expired - Lifetime EP1022351B2 (en) | 1999-01-19 | 1999-12-08 | Plasma sprayed layer on cylinder bores of engine blocks |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04011394A Expired - Lifetime EP1507020B1 (en) | 1999-01-19 | 1999-12-08 | Plasma sprayed layer on cylinder bores of engine blocks |
Country Status (9)
Country | Link |
---|---|
US (2) | US6548195B1 (en) |
EP (2) | EP1507020B1 (en) |
JP (2) | JP3967511B2 (en) |
KR (1) | KR100593342B1 (en) |
AT (2) | ATE267275T1 (en) |
CA (1) | CA2296155C (en) |
DE (2) | DE59914394D1 (en) |
ES (2) | ES2288232T3 (en) |
PT (2) | PT1507020E (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
WO2008031468A2 (en) * | 2006-09-11 | 2008-03-20 | Federal-Mogul Burscheid Gmbh | Wet cylinder sleeve having a cavitation-resistant surface |
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 |
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 |
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 |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6756083B2 (en) * | 2001-05-18 | 2004-06-29 | Höganäs Ab | Method of coating substrate with thermal sprayed metal powder |
JP3910145B2 (en) | 2003-01-06 | 2007-04-25 | 日本発条株式会社 | Thermal spray coating and method for producing the same |
DE10324279B4 (en) * | 2003-05-28 | 2006-04-06 | Daimlerchrysler Ag | Use of FeC alloy to renew the surface of cylinder liners |
CA2514493C (en) * | 2004-09-17 | 2013-01-29 | Sulzer Metco Ag | A spray powder |
GB2421207A (en) * | 2004-12-16 | 2006-06-21 | Cosworth Technology Ltd | Casting with a halogen containing compound provided on the mould surface |
JP4818659B2 (en) * | 2005-08-08 | 2011-11-16 | いすゞ自動車株式会社 | Sliding member for combustion chamber of internal combustion engine and method for manufacturing the same |
KR100878878B1 (en) * | 2007-06-14 | 2009-01-15 | 주식회사뉴테크 | Coating method of engine block liner outside using thermal spray technology |
JP5111965B2 (en) | 2007-07-24 | 2013-01-09 | 株式会社日立製作所 | Storage control device and control method thereof |
JP5257756B2 (en) * | 2007-12-05 | 2013-08-07 | 日産自動車株式会社 | Iron-based thermal spray coating, method for forming the same, and sliding member |
JP5651922B2 (en) * | 2009-03-04 | 2015-01-14 | 日産自動車株式会社 | Cylinder block and thermal spray coating forming method |
JP5455149B2 (en) * | 2009-05-28 | 2014-03-26 | 日産自動車株式会社 | Iron-based thermal spray coating |
CN101818318A (en) * | 2010-05-05 | 2010-09-01 | 北京科技大学 | Method for preparing fine-grained tungsten and molybdenum coatings by atmospheric plasma spraying method |
US20120258254A1 (en) * | 2011-04-06 | 2012-10-11 | Basf Corporation | Methods For Providing High-Surface Area Coatings To Mitigate Hydrocarbon Deposits On Engine And Powertrain Components |
EP2650398B8 (en) * | 2012-04-11 | 2015-05-13 | Oerlikon Metco AG, Wohlen | Spray powder with a superferritic iron base compound and a substrate, in particular brake disc with a thermal spray coating |
DE102012009496B4 (en) | 2012-05-14 | 2017-05-11 | Stahlwerk Ergste Westig Gmbh | chrome steel |
JP6038349B2 (en) * | 2012-12-12 | 2016-12-07 | アーベーベー ターボ システムズ アクチエンゲゼルシャフト | Abrasion resistant layer and method for producing the abrasion resistant layer |
KR101922159B1 (en) * | 2014-11-04 | 2018-11-27 | 현대중공업 주식회사 | Coating material for piston-skirt and coating method for piston-skirt using the same |
US9945318B2 (en) | 2015-12-04 | 2018-04-17 | Hyundai Motor Company | Cylinder block |
CN105543759A (en) * | 2015-12-18 | 2016-05-04 | 合肥中澜新材料科技有限公司 | High-hardness corrosion-resistant wear-resistant engine cylinder inner-wall coating and preparation method thereof |
EP3414356B1 (en) | 2016-02-12 | 2021-04-21 | Oerlikon Surface Solutions AG, Pfäffikon | Tribological system of an internal combustion engine with a coating |
US20190301393A1 (en) * | 2016-05-27 | 2019-10-03 | Oerlikon Metco Ag, Wohlen | A coating method, a thermal coating and a cylinder having a thermal coating |
CN107214341B (en) * | 2017-05-24 | 2019-05-24 | 大连理工大学 | A kind of steel-wear-resistant copper alloy stratiform bush material, its preparation facilities and preparation method |
JP7083295B2 (en) * | 2018-08-22 | 2022-06-10 | トヨタ自動車東日本株式会社 | Sliding member and its manufacturing method |
JP7159111B2 (en) * | 2019-05-28 | 2022-10-24 | 日本ピストンリング株式会社 | Combination of sliding member and lubricating oil |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR735928A (en) * | 1931-05-29 | 1932-11-17 | Manufacturing process for machine parts in light metals with a surface protected against wear | |
DE940082C (en) * | 1950-11-17 | 1956-03-08 | Goetzewerke | Process for the production of cylinder liners |
JPS5864371A (en) * | 1981-10-12 | 1983-04-16 | Honda Motor Co Ltd | Plasma melt-sprayed film |
DE19508687A1 (en) * | 1994-04-08 | 1995-10-12 | Ford Werke Ag | Coating process for engine cylinders of motor vehicles |
EP0715916A2 (en) * | 1994-12-09 | 1996-06-12 | Ford Motor Company Limited | An iron or copper based powder composition |
US5592927A (en) * | 1995-10-06 | 1997-01-14 | Ford Motor Company | Method of depositing and using a composite coating on light metal substrates |
WO1997013884A1 (en) * | 1995-10-06 | 1997-04-17 | Ford Motor Company Limited | Method of depositing composite metal coatings |
US5622753A (en) * | 1996-04-08 | 1997-04-22 | Ford Motor Company | Method of preparing and coating aluminum bore surfaces |
EP0816527A1 (en) * | 1996-06-21 | 1998-01-07 | Ford Motor Company Limited | Method of depositing a thermally sprayed coating onto metal substrates |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB558182A (en) * | 1942-03-09 | 1943-12-24 | British Piston Ring Company Lt | Improvements in and in the manufacture of metal inserts |
GB1390662A (en) * | 1972-05-05 | 1975-04-16 | Ass Eng Ltd | Sintered ferrous machinery components and process for their manufacture |
JPS5432421B2 (en) * | 1973-01-09 | 1979-10-15 | ||
US4060653A (en) * | 1974-02-22 | 1977-11-29 | Kennecott Copper Corporation | Composite wire |
JPS57101662A (en) * | 1980-12-16 | 1982-06-24 | Riken Corp | Sliding component part |
JPH0222444A (en) * | 1988-07-08 | 1990-01-25 | Sanyo Special Steel Co Ltd | Rust-resistant and wear-resistant steel |
US5358547A (en) * | 1993-02-18 | 1994-10-25 | Holko Kenneth H | Cobalt-phosphorous-base wear resistant coating for metallic surfaces |
JPH07243528A (en) * | 1994-03-02 | 1995-09-19 | Teikoku Piston Ring Co Ltd | Combination of sliding member |
US5554278A (en) * | 1994-06-03 | 1996-09-10 | Henderson; Bruce L. | Quick change oil recycler |
CN1068387C (en) * | 1994-06-24 | 2001-07-11 | 普拉塞尔·S·T·技术有限公司 | A process for producing an oxide dispersed mcraly-based coating |
US5723187A (en) * | 1996-06-21 | 1998-03-03 | Ford Global Technologies, Inc. | Method of bonding thermally sprayed coating to non-roughened aluminum surfaces |
AU1655000A (en) * | 1998-11-25 | 2000-06-13 | Joma Chemical As | Material for producing a corrosion- and wear-resistant layer by thermal spraying |
-
1999
- 1999-12-08 AT AT99811122T patent/ATE267275T1/en active
- 1999-12-08 AT AT04011394T patent/ATE365814T1/en active
- 1999-12-08 PT PT04011394T patent/PT1507020E/en unknown
- 1999-12-08 DE DE59914394T patent/DE59914394D1/en not_active Expired - Lifetime
- 1999-12-08 ES ES04011394T patent/ES2288232T3/en not_active Expired - Lifetime
- 1999-12-08 DE DE59909522T patent/DE59909522D1/en not_active Expired - Lifetime
- 1999-12-08 ES ES99811122T patent/ES2221343T5/en not_active Expired - Lifetime
- 1999-12-08 EP EP04011394A patent/EP1507020B1/en not_active Expired - Lifetime
- 1999-12-08 PT PT99811122T patent/PT1022351E/en unknown
- 1999-12-08 EP EP99811122A patent/EP1022351B2/en not_active Expired - Lifetime
- 1999-12-29 US US09/476,009 patent/US6548195B1/en not_active Expired - Lifetime
-
2000
- 2000-01-12 KR KR1020000001269A patent/KR100593342B1/en active IP Right Grant
- 2000-01-17 CA CA002296155A patent/CA2296155C/en not_active Expired - Lifetime
- 2000-01-19 JP JP2000010617A patent/JP3967511B2/en not_active Expired - Lifetime
-
2001
- 2001-10-23 US US10/001,132 patent/US6572931B2/en not_active Expired - Lifetime
-
2007
- 2007-01-18 JP JP2007009236A patent/JP4644687B2/en not_active Expired - Fee Related
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR735928A (en) * | 1931-05-29 | 1932-11-17 | Manufacturing process for machine parts in light metals with a surface protected against wear | |
DE940082C (en) * | 1950-11-17 | 1956-03-08 | Goetzewerke | Process for the production of cylinder liners |
JPS5864371A (en) * | 1981-10-12 | 1983-04-16 | Honda Motor Co Ltd | Plasma melt-sprayed film |
DE19508687A1 (en) * | 1994-04-08 | 1995-10-12 | Ford Werke Ag | Coating process for engine cylinders of motor vehicles |
EP0715916A2 (en) * | 1994-12-09 | 1996-06-12 | Ford Motor Company Limited | An iron or copper based powder composition |
US5592927A (en) * | 1995-10-06 | 1997-01-14 | Ford Motor Company | Method of depositing and using a composite coating on light metal substrates |
WO1997013884A1 (en) * | 1995-10-06 | 1997-04-17 | Ford Motor Company Limited | Method of depositing composite metal coatings |
US5622753A (en) * | 1996-04-08 | 1997-04-22 | Ford Motor Company | Method of preparing and coating aluminum bore surfaces |
EP0816527A1 (en) * | 1996-06-21 | 1998-01-07 | Ford Motor Company Limited | Method of depositing a thermally sprayed coating onto metal substrates |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 7, no. 155 (C - 175) 7 July 1983 (1983-07-07) * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1022351B2 (en) | Plasma sprayed layer on cylinder bores of engine blocks | |
EP1340834B1 (en) | Coated running surfaces of combustion-engine cylinders and process of its manufacture | |
DE3689512T2 (en) | Iron alloy containing molybdenum, copper and boron. | |
DE19637737C2 (en) | Process for the deposition of an iron oxide-containing coating on a light metal substrate | |
DE10046956C2 (en) | Thermally applied coating for piston rings made of mechanically alloyed powders | |
DE2632739C3 (en) | Process for the thermal spraying of a self-adhesive nickel-aluminum or nickel-titanium coating on a metal substrate | |
DE69108963T2 (en) | Wear-resistant titanium nitride coating and method of application. | |
DE69423373T2 (en) | Thermal spraying method for coating cylinder bores for internal combustion engines | |
DE2425358C3 (en) | Method of applying a copper-based reinforcement pad to an aluminum alloy piston | |
DE10308563B3 (en) | Cylinder lining for engines comprises substrate with wear-resistant coating produced by wire-arc spraying which contains martensitic phases and oxygen | |
EP3325685B1 (en) | Method for coating a cylinder barrel of a cylinder crankcase, cylinder crankcase with a coated cylinder barrel and engine | |
EP0858518B1 (en) | Method of producing a slide surface on a light metal alloy | |
EP0858519B1 (en) | Method of producing a sliding surface on a metal workpiece | |
EP0899354A1 (en) | Hyper-eutectic al-si alloy coating respectively an al-si composite | |
DE69902449T2 (en) | METHOD FOR PRODUCING A SLIDING BEARING COATING | |
WO2011147526A1 (en) | Wire-like spray material, functional layer which can be produced therewith and process for coating a substrate with a spray material | |
EP2330228B1 (en) | Spray material, thermal spray layer and cylinder with a thermal spray layer | |
EP0534905A2 (en) | Tools for machining materials | |
DE69216185T2 (en) | Coal body with sprayed metal layer | |
EP1896626B1 (en) | Method for coating a cylinder sleeve | |
DE112014004365B4 (en) | METHOD OF FORMING AN IRON SPRAY COATING AND COATED ELEMENT | |
EP1174524A2 (en) | Surface layer for forming a running layer on a cylinder wall, coating powder therefor and process for producing such a surface layer | |
EP0931172A1 (en) | Coated wear resisting parts for internal combustion engines, specially piston rings, and method for their production | |
DE19601793B4 (en) | Process for coating surfaces | |
DE102015013706A1 (en) | functional layer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 20000816 |
|
AKX | Designation fees paid |
Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
17Q | First examination report despatched |
Effective date: 20030731 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040519 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040519 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040519 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: SULZER MANAGEMENT AG PATENTABTEILUNG/0067 Ref country code: CH Ref legal event code: EP |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20040519 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
REF | Corresponds to: |
Ref document number: 59909522 Country of ref document: DE Date of ref document: 20040624 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040819 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040819 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20040813 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041208 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2221343 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 |
|
ET | Fr: translation filed | ||
PLAQ | Examination of admissibility of opposition: information related to despatch of communication + time limit deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE2 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAQ | Examination of admissibility of opposition: information related to despatch of communication + time limit deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE2 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAQ | Examination of admissibility of opposition: information related to despatch of communication + time limit deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE2 |
|
PLAR | Examination of admissibility of opposition: information related to receipt of reply deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE4 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAQ | Examination of admissibility of opposition: information related to despatch of communication + time limit deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE2 |
|
PLAR | Examination of admissibility of opposition: information related to receipt of reply deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE4 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PLAQ | Examination of admissibility of opposition: information related to despatch of communication + time limit deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE2 |
|
PLAR | Examination of admissibility of opposition: information related to receipt of reply deleted |
Free format text: ORIGINAL CODE: EPIDOSDOPE4 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
26 | Opposition filed |
Opponent name: FORD-WERKE AKTIENGESELLSCHAFT Effective date: 20050218 Opponent name: DAIMLERCHRYSLER AG Effective date: 20050216 |
|
R26 | Opposition filed (corrected) |
Opponent name: FORD-WERKE AKTIENGESELLSCHAFT Effective date: 20050218 Opponent name: DAIMLERCHRYSLER AG Effective date: 20050216 |
|
R26 | Opposition filed (corrected) |
Opponent name: FORD-WERKE AKTIENGESELLSCHAFT Effective date: 20050218 Opponent name: DAIMLERCHRYSLER AG Effective date: 20050216 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: FORD-WERKE AKTIENGESELLSCHAFT Opponent name: DAIMLERCHRYSLER AG |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: FORD-WERKE AKTIENGESELLSCHAFT Opponent name: DAIMLERCHRYSLER AG |
|
PLAF | Information modified related to communication of a notice of opposition and request to file observations + time limit |
Free format text: ORIGINAL CODE: EPIDOSCOBS2 |
|
PLAF | Information modified related to communication of a notice of opposition and request to file observations + time limit |
Free format text: ORIGINAL CODE: EPIDOSCOBS2 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20090225 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: RPEO |
|
NLR2 | Nl: decision of opposition |
Effective date: 20090225 |
|
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Date of ref document: 20090427 Kind code of ref document: T5 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: INTELLECTUAL PROPERTY SERVICES GMBH, CH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: SIVANTOS PTE. LTD., SG Free format text: FORMER OWNER: SULZER METCO AG, CH |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 18 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20181227 Year of fee payment: 20 Ref country code: PT Payment date: 20181129 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20181227 Year of fee payment: 20 Ref country code: FR Payment date: 20181231 Year of fee payment: 20 Ref country code: GB Payment date: 20181221 Year of fee payment: 20 Ref country code: BE Payment date: 20181221 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20190131 Year of fee payment: 20 Ref country code: DE Payment date: 20190228 Year of fee payment: 20 Ref country code: NL Payment date: 20181221 Year of fee payment: 20 Ref country code: IT Payment date: 20181220 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20181228 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59909522 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MK Effective date: 20191207 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20191207 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK07 Ref document number: 267275 Country of ref document: AT Kind code of ref document: T Effective date: 20191208 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MK Effective date: 20191208 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20191219 Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20191207 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20220128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20191209 |