EP1917370B1 - Fil a base de pt-ir durci par dispersion d'oxyde et d'autres alliages, a surface amelioree pour des electrodes de bougies d'allumage - Google Patents
Fil a base de pt-ir durci par dispersion d'oxyde et d'autres alliages, a surface amelioree pour des electrodes de bougies d'allumage Download PDFInfo
- Publication number
- EP1917370B1 EP1917370B1 EP06776674A EP06776674A EP1917370B1 EP 1917370 B1 EP1917370 B1 EP 1917370B1 EP 06776674 A EP06776674 A EP 06776674A EP 06776674 A EP06776674 A EP 06776674A EP 1917370 B1 EP1917370 B1 EP 1917370B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wire
- strip
- platinum
- alloy
- alloyed
- 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.)
- Not-in-force
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 33
- 239000000956 alloy Substances 0.000 title claims abstract description 33
- 239000006185 dispersion Substances 0.000 title claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 41
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000002093 peripheral effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910001020 Au alloy Inorganic materials 0.000 claims 1
- 229910000629 Rh alloy Inorganic materials 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 239000003353 gold alloy Substances 0.000 claims 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910001260 Pt alloy Inorganic materials 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910002835 Pt–Ir Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T13/00—Sparking plugs
- H01T13/20—Sparking plugs characterised by features of the electrodes or insulation
- H01T13/39—Selection of materials for electrodes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
- Y10S75/95—Consolidated metal powder compositions of >95% theoretical density, e.g. wrought
- Y10S75/951—Oxide containing, e.g. dispersion strengthened
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12875—Platinum group metal-base component
Definitions
- the present invention relates to platinum-group metal platelets or wires for use as electrodes in spark plugs and to methods of making same.
- refractory base metal alloys e.g., W
- intercalated oxides of rare earth elements are used to minimize spark erosion wear in service.
- Pt-based alloys with additions of Ir, Ru, W, Mo and / or Re. These alloying elements share the common feature that they oxidize much more easily than platinum and form volatile oxides upon oxidation.
- Oxide-dispersion-hardened Pt-Ir and other Pt alloys which can be prepared by the internal oxidation of non-precious metal components ( DE 197 14 365 . DE 197 58 724 C2 and DE 100 46 456 ). However, it has been found in studies that these materials have significant disadvantages when they should be used as electrode materials in spark plugs.
- EP 447 820 discloses a composite wire having a core of a Pt-Ir alloy and a sheath of platinum.
- Decisive is a significant leaning of at least one volatile component in the wire or belt surface.
- a depletion of one quarter is sufficient to achieve the effect according to the invention.
- the depletion is preferably greater than a quarter, in particular more than half and preferably more than 90%.
- the depletion refers to the initial mass or number of moles of the depleted component.
- a tape or wire whose composition is based on platinum or palladium.
- the strip or wire is made of an oxide-dispersion-hardened alloy doped with non-precious metal additives.
- the alloy may additionally contain minor group elements such as iron, cobalt, nickel, rhenium, tungsten, tantalum, hafnium, lanthanum, molybdenum, niobium, zirconium, yttrium, titanium, scandium and gold, as well as lanthanides as subordinate alloy constituents.
- the tape or wire has a peripheral zone in which the more volatile components of the alloy are emaciated and their volatility is no longer critical under oxidic conditions, so that the volatile oxide formers in the belt or wire are protected from further oxidation.
- the emaciated edge zone is relatively soft and allows a crack-free further processing of the tape or wire. It is also important that the coat provides protection against further thinning of the volatile constituents under oxidic conditions or can be converted into such a protection.
- an embodiment of the invention is based on first producing a jacket with a porous zone having a thickness of 20 to 300 microns.
- the porous zone can be converted into a dense soft outer layer with a thickness of 1 to 50 ⁇ m, in particular to a thickness of 5 to 20 ⁇ m.
- the band or the wire can in this case have a diameter of 0.05 to 5 mm, in particular 0.1 to 2 mm.
- the layer thickness is 0.1 to 5% of the diameter of the strip or wire.
- the layer thickness of the dense zone is preferably 0.5 to 5% of the diameter of the band or the wire, in particular 1 to 2%.
- the more volatile constituents are preferably no longer present in the skin surface or have a concentration gradient in the skin, so that a concentration gradient from the skin inside to the skin outside a decrease in the more volatile component of at least 25%, in particular 50%, preferably in the order of magnitude is present.
- the decrease is relative and refers to the internal concentration, especially in terms of mass or number of moles.
- the decrease is relative to the internal concentration, i. at a 25% decrease, the external concentration is 75% of the internal concentration; with a decrease of 50% still 50% and with a decrease by one order of magnitude still a fraction of an order reduced fraction.
- the concentration data can be based on mass or mol.
- a thin layer of substantially pure platinum Pt content> 90%, preferably> 95%) on the surface of the belt or wire or outer surface of the molded parts significantly reduces the tendency to crack during processing can be.
- the word "lateral surface” is here used in the sense of a lateral surface of a cylinder synonymous with the surface of the cylinder-like wire or the band.
- Typical layer thicknesses are 0.1-3% of the thickness of the strip or the diameter of the wire.
- the layer of largely pure Pt acts as a diffusion barrier, which largely prevents the further loss of the alloying elements by oxidation and evaporation of the oxide.
- the portion of the tape or wire or the molding can be used directly as an electrode, without the Pt layer affecting the function of the electrode.
- the emaciated rim significantly improves the corrosion resistance of the belt or wire.
- a method for producing a strip or a wire of an oxide dispersion-hardened platinum-group-metal-based alloy according to the present invention is to thermally form a porous outer layer by thermally treating this strip or wire on that strip or a wire of a given alloy, and forming the porous outer layer by forming to densify to an impermeable layer.
- the Pt layer can be conveniently produced in sifu .
- the alloying element diffuses toward the surface where it oxidizes and vaporizes in the form of a volatile oxide. This results in a soft, porous layer of largely pure Pt at the surface.
- the porous layer is compacted to form an impermeable layer, which acts as a diffusion barrier. The deformability of the oxide dispersion-hardened Pt alloy is significantly improved by this layer.
- Proven ribbons or wires based on platinum or palladium alloys contain (in% by weight elements which form volatile oxides):
- Ir 0,3-50% prefers 10-30% Ru 0,3-30% prefers 3-20% re 0.3-20% prefers 3-10% W 0.3-10% prefers 1-6% Not a word 0.3-10% prefers 1-6% ⁇ In total, at least 3% and a maximum of 35%.
- Zr 0.05-3% prefers 0.1-1% Ce 0.05-3% prefers 0.1-1% Y 0.005-0.3% prefers 0.01-0.1% sc 0.005-0.3% prefers 0.01-0.1%
- Oxidation treatment to produce the surface zone 1450 to 1750 ° C, preferably 1450 to 1650 ° C.
- a dispersion strengthened platinum material was prepared according to DE 100 46 456 and DE 197 14 365 provided.
- an alloy of 3.5 kg Pt and 1.5 kg Ir (corresponding to 5 kg of the alloy Ptlr30) was melted under vacuum in a zirconium oxide crucible. After melting and degassing, the melt was doped by means of 36 g of a master alloy consisting of Pt with 28% Zr and 2.8% Sc and poured in a mold into a billet with the approximate dimensions 40 mm ⁇ 40 mm ⁇ 150 mm. Analysis of the billet revealed a composition of PtIr30 with 1850 ppm Zr and 175 ppm Sc.
- the ingot was planed to eliminate casting defects and forged at 1000 ° C into a 15 mm x 15 mm cross-section bar. Subsequently, the bar was rolled at 1000 ° C to a square wire (4 mm x 4 mm). This was outsourced for 10 days at 1000 ° C under air atmosphere.
- hot gas extraction analysis LECO method
- the oxygen content was determined to be 735 ppm. With complete oxidation of the Zr doping to ZrO 2 and the Sc doping to Sc 2 O 3 , the oxygen content would be 742 ppm.
- the wire was split and the individual wire sections treated differently.
- the first wire section was aged for 8 hours at 1600 ° C under air atmosphere.
- the cross-section metallographic examination showed a porous zone about 120 ⁇ m thick on the surface.
- the investigation of this zone by means of energy dispersive analysis in the scanning electron microscope revealed an Ir content which decreased from 19% to 3% from the inside to the outside.
- This wire section was further rolled as a square profile at 700 ° C without problems to a cross section of 2.4 mm x 2.4 mm.
- a sample was taken from the wire, which was examined by metallographic cross-section.
- the investigation shows a dense outer layer with uniformly fine-grained microstructure and an average layer thickness of 42 ⁇ m.
- the remaining annealed wire was further processed on a conventional wire drawing machine at 25 ° C. It could be pulled without difficulty to a diameter of 0.6 mm.
- Another cross-section survey showed a dense, soft outer layer about 8 microns thick. The wire could already be bent over a radius of 1 mm by 180 ° in the hard-drawn state, without cracks having occurred.
- the second section was further rolled without further heat treatment as a square profile at 700 ° C. Even after slight deformation pronounced transverse cracks occurred.
- the further processing was stopped at a cross section of about 3.5 mm x 3.5 mm.
- the third section was stored for 8 h at 1600 ° C under argon atmosphere and further rolled as a square profile at 700 ° C.
- First transverse cracks only occurred at a cross section of about 2.8 mm x 2.8 mm.
- Example 2 Analogously to Example 1, an alloy of PtIr20 with dopings of 3200 ppm Zr and 350 ppm Y was prepared. For the cross section 4 mm x 4 mm, the material was aged for 15 days at 1000 ° C in air atmosphere. The processing was carried out according to the o.a. first wire section described sequence.
- An alloy of PtIr30 doped with 5000 ppm Ce was also prepared analogously to Example 1 and processed into a wire with a diameter of 0.7 mm.
- An alloy of PtRu10 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and processed into a wire with a diameter of 0.6 mm.
- An alloy of PtRe10 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and made into a wire with a diameter of 0.6 mm.
- An alloy of PtW5 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and made into a wire with a diameter of 0.6 mm.
- An alloy of PtMo5 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and processed into a wire with a diameter of 0.6 mm.
- An alloy of PtIr18W1 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and made into a wire with a diameter of 0.6 mm.
- An alloy of PtIr10Ru5 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and made into a wire with a diameter of 0.6 mm.
- An alloy of PtRh10Ru5 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and processed into a wire with a diameter of 0.6 mm.
- An alloy of PtAu3Ir5 doped with 1800 ppm Zr and 200 ppm Sc was also prepared analogously to Example 1 and processed into a wire with a diameter of 0.6 mm.
- a dispersion strengthened platinum material was prepared according to DE 100 46 456 and DE 197 14 365 provided.
- an alloy of 4.0 kg Pt and 1.0 kg Ir (corresponding to 5 kg of the alloy PtIr20) was melted under vacuum in a zirconium oxide crucible. After melting and degassing, the melt was doped by means of 36 g of a master alloy consisting of Pt with 28% Zr and 2.8% Sc and poured into a mold into a billet with the approximate dimensions 40 mm ⁇ 40 mm ⁇ 150 mm. Analysis of the billet revealed a composition of PtIr20 with 1850 ppm Zr and 175 ppm Sc.
- the billet was planed to eliminate casting defects and forged at 1000 ° C to a bar with a cross-section of 20 mm x 10 mm. Subsequently, the bar was rolled at 1000 ° C to a thickness of 4 mm.
- the tape was aged for 12 days at 1000 ° C under air atmosphere. By hot gas extraction analysis (LECO method), the oxygen content was determined to be 725 ppm. With complete oxidation of the Zr doping to ZrO 2 as well as the Sc doping to Sc 2 O 3 , the oxygen content would be 742 ppm.
- the tape was divided into three parts and the individual tape sections treated differently.
- the first band section was aged for 8 h at 1600 ° C under air atmosphere.
- the cross-section metallographic examination showed a porous zone about 120 ⁇ m thick on the surface. Examination of this zone by means of energy dispersive analysis in a scanning electron microscope revealed an Ir content which decreased from 14% to 2% from the inside out.
- This strip section was further rolled at 700 ° C. without problems to a thickness of 1.5 mm. After another annealing for 10 min at 1000 ° C under air atmosphere, a sample was taken from the tape, which was examined metallographically in transverse section. The investigation shows a dense outer layer with uniformly fine-grained microstructure and an average layer thickness of 30 ⁇ m.
- a comparison of the material hardness by means of micro hardness testing according to Vickers with a load of 25 g gave a hardness of 225 for the inner area of the strip cross section and a hardness of 145 for the middle of the outer layer.
- the cross section was examined by means of energy dispersive analysis in the scanning electron microscope. The iridium content decreased from 20% in the interior of the sample to 5% below the outside surface. The remaining annealed strip was further rolled at 25 ° C. It could be rolled without difficulty to a thickness of 0.4 mm.
- Another cross-section survey showed a dense, soft outer layer about 7 ⁇ m thick. Already in the hard-drawn state, the strip could be bent through 180 ° over a radius of 1 mm without causing any cracks.
- the second section was further rolled without further heat treatment at 700 ° C. Even after slight deformation, pronounced cracks occurred. Further processing was stopped at a thickness of 2.8 mm.
- Example 14 An alloy of PtW5 doped with 3200 ppm Zr and 350 ppm Sc was also prepared analogously to Example 1 and made into a strip 0.3 mm thick. From this band discs of diameter 1.5 mm were punched, which were used as spark plug electrodes in car engines. The tapes of Example 14 passed the tests made in Example 13 in an analogous manner.
- the third section was stored for 8 hours at 1600 ° C. under an argon atmosphere and further rolled at 700 ° C. First cracks first appeared at a thickness of about 2.2 m.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Spark Plugs (AREA)
- Powder Metallurgy (AREA)
- Ignition Installations For Internal Combustion Engines (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Claims (8)
- Bande ou câble constitué d'un alliage durci par dispersion d'oxyde à base de platine ou de palladium ou d'un mélange de platine et de palladium, la part massique en platine et en palladium dans la somme étant d'au moins 50 % en poids et lequel contient un ou plusieurs agents formant un oxyde, lequel ou lesquels forme respectivement forment des oxydes facilement volatils choisis parmi0,3 - 50 % en poids d'iridium,0,3 - 30 % en poids de ruthénium,0,3 - 20 % en poids de rhénium,0,3 - 10 % en poids de tungstène et0,3 - 10 % en poids de molybdène,au total au moins 3 % et au maximum 35 %, caractérisé en ce que la section transversale de la bande ou du câble présente une zone de bord qui représente de 0,1 à 5 % de l'épaisseur de la bande ou du câble, dans laquelle au moins un de ces agents formant un oxyde, lequel forme des oxydes relativement facilement volatils, est dilué à au moins un quart.
- Bande alliée ou câble allié selon la revendication 1, caractérisée en ce que la bande ou le câble présente un enrobage de platine ou de palladium ou d'un alliage de platine-rhodium ou d'un alliage de platine-or.
- Bande alliée ou câble allié selon l'une quelconque des revendications 1 ou 2, caractérisée en ce qu'une zone de bord poreuse présente une épaisseur de 20 à 300 µm.
- Bande alliée ou câble allié selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que la bande ou le câble présente une épaisseur de 0,05 à 5 mm et une zone de bord dense souple présente une épaisseur de 1 à 50 µm.
- Bande alliée ou câble allié selon l'une quelconque des revendications 2 à 4, caractérisée en ce que les constituants de l'alliage du platine dans la zone de bord présentent de l'intérieur vers l'extérieur une chute de concentration avec une diminution jusqu'à la moitié ou moins.
- Procédé pour la préparation d'une bande ou d'un câble d'un alliage durci par dispersion d'oxyde à base de platine ou de palladium ou d'un mélange de platine-palladium selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on produit thermiquement sur une bande ou un câble de l'alliage durci par dispersion d'oxyde une peau poreuse et on épaissit la peau poreuse par déformation en une peau souple ou imperméable.
- Utilisation d'une bande ou d'un câble selon l'une quelconque des revendications 1 à 5 comme électrode de bougies d'allumage.
- Utilisation d'une bande ou d'un câble préparé selon la revendication 6 comme électrode de bougie d'allumage.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI200630345T SI1917370T1 (sl) | 2005-08-15 | 2006-08-08 | Ĺ˝ica iz z oksidno disperzijo ojaäśene zlitine platine in iridija ter drugih zlitin z izboljĺ ano povrĺ ino za elektrode vĺ˝igalnih sveäśk |
| PL06776674T PL1917370T3 (pl) | 2005-08-15 | 2006-08-08 | Drut oparty na Pt-Ir, utwardzany dyspersją tlenkową oraz inne stopy o ulepszonej powierzchni na elektrody świec zapłonowych |
| CY20091100738T CY1109237T1 (el) | 2005-08-15 | 2009-07-14 | Συρμα με βαση κραματα pt-ir ή αλλα που εχει σκληρυνθει δια διασπορας οξειδιων εφοδιασμενο με βελτιωμενη επιφανεια δια ηλεκτροδια μπουζι |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005038772A DE102005038772B4 (de) | 2005-08-15 | 2005-08-15 | Draht aus oxiddispersionsgehärteten Pt-lr- und anderen Legierungen mit verbesserter Oberfläche für Zündkerzenelektroden |
| DE102005056619 | 2005-11-25 | ||
| PCT/EP2006/007835 WO2007019990A1 (fr) | 2005-08-15 | 2006-08-08 | Fil a base de pt-ir durci par dispersion d'oxyde et d'autres alliages, a surface amelioree pour des electrodes de bougies d'allumage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1917370A1 EP1917370A1 (fr) | 2008-05-07 |
| EP1917370B1 true EP1917370B1 (fr) | 2009-04-15 |
Family
ID=37312024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06776674A Not-in-force EP1917370B1 (fr) | 2005-08-15 | 2006-08-08 | Fil a base de pt-ir durci par dispersion d'oxyde et d'autres alliages, a surface amelioree pour des electrodes de bougies d'allumage |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US7736752B2 (fr) |
| EP (1) | EP1917370B1 (fr) |
| JP (1) | JP5294859B2 (fr) |
| AT (1) | ATE428812T1 (fr) |
| CY (1) | CY1109237T1 (fr) |
| DE (1) | DE502006003473D1 (fr) |
| DK (1) | DK1917370T3 (fr) |
| ES (1) | ES2326042T3 (fr) |
| PL (1) | PL1917370T3 (fr) |
| PT (1) | PT1917370E (fr) |
| SI (1) | SI1917370T1 (fr) |
| WO (1) | WO2007019990A1 (fr) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007007873A1 (de) * | 2007-02-14 | 2008-08-21 | W.C. Heraeus Gmbh | Oxiddispersionsgehärteter, durch innere Oxidation hergestellter Pt-, PtRh- oder PtAu-Werkstoff mit hohem Oxidanteil und guter Duktilität |
| WO2009086723A1 (fr) * | 2008-01-04 | 2009-07-16 | Wuxi Yingtepai Metal Product Co., Ltd. | Alliage de pd-au renforcé par une dispersion d'oxyde de zirconium et d'oxyde d'yttrium et son procédé de fabrication |
| US20090302732A1 (en) * | 2008-03-07 | 2009-12-10 | Lykowski James D | Alloys for spark ignition device electrode spark surfaces |
| US7969078B2 (en) * | 2008-05-19 | 2011-06-28 | Federal Mogul Ignition Company | Spark ignition device for an internal combustion engine and sparking tip therefor |
| DE202008013345U1 (de) * | 2008-10-07 | 2008-12-24 | Siemens Aktiengesellschaft | Metallischer Pin für Feingussverfahren und Gussform |
| JP5325220B2 (ja) * | 2009-01-23 | 2013-10-23 | 日本特殊陶業株式会社 | スパークプラグ |
| WO2011125267A1 (fr) * | 2010-04-02 | 2011-10-13 | 日本特殊陶業株式会社 | Bougie d'allumage |
| DE102014210984A1 (de) * | 2014-06-10 | 2015-12-17 | Robert Bosch Gmbh | Zündkerzenelektrode, Verfahren zu deren Herstellung und Zündkerze |
| EP3971311B1 (fr) * | 2020-09-17 | 2022-07-06 | Heraeus Deutschland GmbH & Co. KG | Alliage de métaux précieux durci par dispersion amélioré |
| EP3978884B1 (fr) * | 2020-10-02 | 2024-05-29 | Heraeus Precious Metals GmbH & Co. KG | Fil ayant une composition platine permettant de mettre en contact des capteurs de température |
| WO2025073358A1 (fr) * | 2023-10-04 | 2025-04-10 | Heraeus Precious Metals Gmbh & Co. Kg | Utilisation d'un alliage de platine pour des électrodes de bougie d'allumage et pour des pièces d'extrémité d'électrode de bougie d'allumage |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3868530A (en) * | 1973-07-05 | 1975-02-25 | Champion Spark Plug Co | Spark plug |
| NL8100238A (nl) | 1980-01-25 | 1981-08-17 | Johnson Matthey Co Ltd | Legering, werkwijze voor het bereiden hiervan en toepassing van de legering. |
| DE3832342C1 (en) * | 1988-09-23 | 1989-07-20 | W.C. Heraeus Gmbh, 6450 Hanau, De | Platinum-jacketed wire, method for production of a platinum-jacketed wire and use of a platinum-jacketed wire |
| DE4009366A1 (de) * | 1990-03-23 | 1991-09-26 | Heraeus Gmbh W C | Verfahren zur herstellung eines metallischen verbunddrahtes |
| JPH04235740A (ja) * | 1991-01-18 | 1992-08-24 | Tanaka Kikinzoku Kogyo Kk | 触媒網 |
| GB9120161D0 (en) * | 1991-09-20 | 1991-11-06 | Johnson Matthey Plc | New pinning wire products |
| GB2299813A (en) * | 1995-04-08 | 1996-10-16 | Ford Motor Co | Spark plug electrode |
| DE19645155C2 (de) * | 1996-11-02 | 2001-09-13 | Heraeus Gmbh W C | Elektrode für die Implantation in Körpergewebe, Verfahren zu ihrer Herstellung und ihre Verwendung (I) |
| DE19758724C2 (de) * | 1997-04-08 | 2002-12-12 | Heraeus Gmbh W C | Dispersionsverfestigter Platin-Gold-Werkstoff, Verfahren zu seiner Herstellung und seine Verwendung |
| DE10040591C1 (de) * | 2000-08-15 | 2001-11-08 | Heraeus Gmbh W C | Verfahren zur Herstellung einer Beschichtung auf einem feuerfesten Bauteil und deren Verwendung |
| DE10046456C2 (de) * | 2000-09-18 | 2003-04-10 | Heraeus Gmbh W C | Durch feinverteilte, kleine Teilchen aus Unedelmetalloxid dispersionsverfestigter, goldfreier Platin-Werkstoff |
| US6664719B2 (en) * | 2001-03-28 | 2003-12-16 | Ngk Spark Plug Co., Ltd. | Spark plug |
-
2006
- 2006-08-08 DK DK06776674T patent/DK1917370T3/da active
- 2006-08-08 EP EP06776674A patent/EP1917370B1/fr not_active Not-in-force
- 2006-08-08 PL PL06776674T patent/PL1917370T3/pl unknown
- 2006-08-08 ES ES06776674T patent/ES2326042T3/es active Active
- 2006-08-08 WO PCT/EP2006/007835 patent/WO2007019990A1/fr not_active Ceased
- 2006-08-08 PT PT06776674T patent/PT1917370E/pt unknown
- 2006-08-08 SI SI200630345T patent/SI1917370T1/sl unknown
- 2006-08-08 DE DE502006003473T patent/DE502006003473D1/de active Active
- 2006-08-08 AT AT06776674T patent/ATE428812T1/de active
- 2006-08-08 JP JP2008526409A patent/JP5294859B2/ja not_active Expired - Fee Related
-
2008
- 2008-02-14 US US12/031,292 patent/US7736752B2/en not_active Expired - Fee Related
-
2009
- 2009-07-14 CY CY20091100738T patent/CY1109237T1/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007019990A1 (fr) | 2007-02-22 |
| EP1917370A1 (fr) | 2008-05-07 |
| SI1917370T1 (sl) | 2009-10-31 |
| JP2009504917A (ja) | 2009-02-05 |
| US7736752B2 (en) | 2010-06-15 |
| DK1917370T3 (da) | 2009-08-17 |
| CY1109237T1 (el) | 2014-07-02 |
| US20080295925A1 (en) | 2008-12-04 |
| PL1917370T3 (pl) | 2009-09-30 |
| DE502006003473D1 (de) | 2009-05-28 |
| ATE428812T1 (de) | 2009-05-15 |
| PT1917370E (pt) | 2009-07-20 |
| ES2326042T3 (es) | 2009-09-29 |
| JP5294859B2 (ja) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7736752B2 (en) | Pt/Pd alloy wires, strips or reshaped parts hardened by oxide dispersion, and process of producing the same | |
| DE112012002699B4 (de) | Zündkerze und Verfahren zum Herstellen einer Elektrode einer Zündkerze | |
| EP1964938B1 (fr) | Matière première platine, platine Rh- ou platine Au fabriquée par oxydation interne, durcie par dispersion d'oxyde et ayant une teneur élevée en oxyde et une bonne ductilité | |
| DE19714365A1 (de) | Dispersionsverfestiger Platin-Werkstoff, Verfahren zu seiner Herstellung und seine Verwendung | |
| DE112012004420B4 (de) | Verfahren zum Herstellen einer Elektrode einer Zündkerze und Zündkerzen-Herstellungsverfahren | |
| EP0947595B1 (fr) | Procédé de préparation d'un article soudé, en particulier un tube, en matériau à base de platine renforcé par dispersion | |
| EP1029100B1 (fr) | Produit pourvu d'un systeme stratifie pour la protection contre un gaz chaud agressif | |
| DE3780082T2 (de) | Rostfreier chrom-aluminium-stahl mit hoher bestaendigkeit gegen oxydation und abblaetterung und folien aus chrom-aluminium-stahl fuer katalysatortraeger in katalytischen konvertern. | |
| EP3054023B1 (fr) | Haute température alliage de ti-al riche en aluminium | |
| EP0241807A2 (fr) | Revêtement résistant à haute température | |
| EP3333281A1 (fr) | Couche de protection haute température pour alliages à base d'aluminures de titane | |
| DE3700659A1 (de) | Feinkoerniger versproedungsfester tantaldraht | |
| EP2514052B2 (fr) | Electrode de bougie d'allumage produite à partir d'un matériau d'électrode amélioré | |
| DE69109140T2 (de) | Spritzauftragsmaterial und damit beschichteter Gegenstand mit ausgezeichnetem Hochtemperatur-Verschleisswiderstand. | |
| DE102005038772B4 (de) | Draht aus oxiddispersionsgehärteten Pt-lr- und anderen Legierungen mit verbesserter Oberfläche für Zündkerzenelektroden | |
| DE69805242T2 (de) | Titanaluminidlegierung | |
| EP3020847B1 (fr) | Couche de protection contre l'oxydation pour matières en TiAl et son procédé de fabrication | |
| EP3978884B1 (fr) | Fil ayant une composition platine permettant de mettre en contact des capteurs de température | |
| EP2450463B1 (fr) | Alliage d'aluminium | |
| DE10332078B3 (de) | Verfahren zum Zerspanen eines Werkstücks aus einer Titan-Basislegierung | |
| EP1230429B1 (fr) | Procede de realisation d'un element recouvert d'une couche | |
| DE19941228B4 (de) | Eisenaluminidbeschichtung und deren Verwendung | |
| EP3763845B1 (fr) | Alliage de magnesium et son procédé de fabrication | |
| EP2697404B1 (fr) | Alliage pour electrode de bougie d'allumage, bougie d'allumage et procede pour la fabrication | |
| WO2025073358A1 (fr) | Utilisation d'un alliage de platine pour des électrodes de bougie d'allumage et pour des pièces d'extrémité d'électrode de bougie d'allumage |
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 |
|
| 17P | Request for examination filed |
Effective date: 20080111 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| 17Q | First examination report despatched |
Effective date: 20080509 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| DAX | Request for extension of the european patent (deleted) | ||
| 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 BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REF | Corresponds to: |
Ref document number: 502006003473 Country of ref document: DE Date of ref document: 20090528 Kind code of ref document: P |
|
| REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20090713 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
| REG | Reference to a national code |
Ref country code: GR Ref legal event code: EP Ref document number: 20090401780 Country of ref document: GR |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2326042 Country of ref document: ES Kind code of ref document: T3 |
|
| REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
| REG | Reference to a national code |
Ref country code: EE Ref legal event code: FG4A Ref document number: E003520 Country of ref document: EE Effective date: 20090715 |
|
| REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E006293 Country of ref document: HU |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20100118 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: TD Effective date: 20111102 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: HANS-CHRISTIAN KUEHN, DE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 502006003473 Country of ref document: DE Owner name: HERAEUS DEUTSCHLAND GMBH & CO. KG, DE Free format text: FORMER OWNER: W.C. HERAEUS GMBH, 63450 HANAU, DE Effective date: 20111219 Ref country code: DE Ref legal event code: R081 Ref document number: 502006003473 Country of ref document: DE Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG, DE Free format text: FORMER OWNER: W.C. HERAEUS GMBH, 63450 HANAU, DE Effective date: 20111219 Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: KUEHN, HANS-CHRISTIAN, DE Effective date: 20111219 Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: EULER, MATTHIAS, DR., DE Effective date: 20111219 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG Free format text: W.C. HERAEUS GMBH#HERAEUSSTRASSE 12 - 14#63450 HANAU (DE) -TRANSFER TO- HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG#HERAEUSSTRASSE 12-14#63450 HANAU (DE) |
|
| REG | Reference to a national code |
Ref country code: EE Ref legal event code: GB1A Ref document number: E003520 Country of ref document: EE |
|
| REG | Reference to a national code |
Ref country code: HU Ref legal event code: GB9C Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG, DE Free format text: FORMER OWNER(S): W.C. HERAEUS GMBH, DE Ref country code: HU Ref legal event code: FH1C Free format text: FORMER REPRESENTATIVE(S): PINTZ ES TARSAI SZABADALMI ES VEDJEGY IRODA, HU |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO.KG Effective date: 20120503 |
|
| REG | Reference to a national code |
Ref country code: SI Ref legal event code: SP73 Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO.KG; DE Effective date: 20120530 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: PC Ref document number: 428812 Country of ref document: AT Kind code of ref document: T Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG, DE Effective date: 20120518 |
|
| REG | Reference to a national code |
Ref country code: SK Ref legal event code: TC4A Ref document number: E 5750 Country of ref document: SK Owner name: HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG, HA, DE Effective date: 20120816 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20130822 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20130821 Year of fee payment: 8 Ref country code: NL Payment date: 20130815 Year of fee payment: 8 Ref country code: RO Payment date: 20130730 Year of fee payment: 8 Ref country code: CH Payment date: 20130821 Year of fee payment: 8 Ref country code: SK Payment date: 20130806 Year of fee payment: 8 Ref country code: IS Payment date: 20130719 Year of fee payment: 8 Ref country code: HU Payment date: 20130821 Year of fee payment: 8 Ref country code: SI Payment date: 20130723 Year of fee payment: 8 Ref country code: PT Payment date: 20130208 Year of fee payment: 8 Ref country code: EE Payment date: 20130813 Year of fee payment: 8 Ref country code: AT Payment date: 20130813 Year of fee payment: 8 Ref country code: FI Payment date: 20130813 Year of fee payment: 8 Ref country code: IE Payment date: 20130829 Year of fee payment: 8 Ref country code: BG Payment date: 20130813 Year of fee payment: 8 Ref country code: SE Payment date: 20130821 Year of fee payment: 8 Ref country code: MC Payment date: 20130813 Year of fee payment: 8 Ref country code: LT Payment date: 20130723 Year of fee payment: 8 Ref country code: ES Payment date: 20130816 Year of fee payment: 8 Ref country code: CZ Payment date: 20130802 Year of fee payment: 8 Ref country code: GR Payment date: 20130822 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20130724 Year of fee payment: 8 Ref country code: LV Payment date: 20130813 Year of fee payment: 8 Ref country code: FR Payment date: 20130823 Year of fee payment: 8 Ref country code: GB Payment date: 20130821 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20130829 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20130823 Year of fee payment: 8 Ref country code: CY Payment date: 20130726 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20131105 Year of fee payment: 8 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: CJ Effective date: 20140630 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20150209 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: KUEHN, HANS-CHRISTIAN, DE |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20150301 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MM4D Effective date: 20140808 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP Effective date: 20140831 |
|
| 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: 20140808 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140901 |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: KUEHN, HANS-CHRISTIAN, DE Effective date: 20150223 Ref country code: DE Ref legal event code: R081 Ref document number: 502006003473 Country of ref document: DE Owner name: HERAEUS DEUTSCHLAND GMBH & CO. KG, DE Free format text: FORMER OWNER: HERAEUS MATERIALS TECHNOLOGY GMBH & CO. KG, 63450 HANAU, DE Effective date: 20150223 Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: EULER, MATTHIAS, DR., DE Effective date: 20150223 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 428812 Country of ref document: AT Kind code of ref document: T Effective date: 20140808 Ref country code: EE Ref legal event code: MM4A Ref document number: E003520 Country of ref document: EE Effective date: 20140831 |
|
| REG | Reference to a national code |
Ref country code: GR Ref legal event code: ML Ref document number: 20090401780 Country of ref document: GR Effective date: 20150304 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20140808 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS 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: 20150301 Ref country code: BG Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150331 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140831 Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: LT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140831 Ref country code: CZ Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150301 Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150209 Ref country code: SK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140831 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: EE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140831 Ref country code: HU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140809 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 |
|
| REG | Reference to a national code |
Ref country code: SK Ref legal event code: MM4A Ref document number: E 5750 Country of ref document: SK Effective date: 20140808 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140809 Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150304 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: CY Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: SI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140809 Ref country code: LV Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150430 Ref country code: SI Ref legal event code: KO00 Effective date: 20150408 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140831 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140901 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20150925 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20140809 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 |
|
| REG | Reference to a national code |
Ref country code: PL Ref legal event code: LAPE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140808 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20170822 Year of fee payment: 12 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 502006003473 Country of ref document: DE Representative=s name: EULER, MATTHIAS, DR., DE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502006003473 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190301 |