EP1917370B1 - Draht aus oxiddispersionsgehärtetem pt-ir- und anderen legierungen mit verbesserter oberfläche für zündkerzenelektroden - Google Patents

Draht aus oxiddispersionsgehärtetem pt-ir- und anderen legierungen mit verbesserter oberfläche für zündkerzenelektroden Download PDF

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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
Application number
EP06776674A
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German (de)
English (en)
French (fr)
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EP1917370A1 (de
Inventor
Harald Manhardt
Carsten Mohr
David Lupton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WC Heraus GmbH and Co KG
Original Assignee
WC Heraus GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102005038772A external-priority patent/DE102005038772B4/de
Application filed by WC Heraus GmbH and Co KG filed Critical WC Heraus GmbH and Co KG
Priority to SI200630345T priority Critical patent/SI1917370T1/sl
Priority to PL06776674T priority patent/PL1917370T3/pl
Publication of EP1917370A1 publication Critical patent/EP1917370A1/de
Application granted granted Critical
Publication of EP1917370B1 publication Critical patent/EP1917370B1/de
Priority to CY20091100738T priority patent/CY1109237T1/el
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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.

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  • 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)
EP06776674A 2005-08-15 2006-08-08 Draht aus oxiddispersionsgehärtetem pt-ir- und anderen legierungen mit verbesserter oberfläche für zündkerzenelektroden Not-in-force EP1917370B1 (de)

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 (de) 2005-08-15 2006-08-08 Draht aus oxiddispersionsgehärtetem pt-ir- und anderen legierungen mit verbesserter oberfläche für zündkerzenelektroden

Publications (2)

Publication Number Publication Date
EP1917370A1 EP1917370A1 (de) 2008-05-07
EP1917370B1 true EP1917370B1 (de) 2009-04-15

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EP06776674A Not-in-force EP1917370B1 (de) 2005-08-15 2006-08-08 Draht aus oxiddispersionsgehärtetem pt-ir- und anderen legierungen mit verbesserter oberfläche für zündkerzenelektroden

Country Status (12)

Country Link
US (1) US7736752B2 (el)
EP (1) EP1917370B1 (el)
JP (1) JP5294859B2 (el)
AT (1) ATE428812T1 (el)
CY (1) CY1109237T1 (el)
DE (1) DE502006003473D1 (el)
DK (1) DK1917370T3 (el)
ES (1) ES2326042T3 (el)
PL (1) PL1917370T3 (el)
PT (1) PT1917370E (el)
SI (1) SI1917370T1 (el)
WO (1) WO2007019990A1 (el)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
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 (zh) * 2008-01-04 2009-07-16 Wuxi Yingtepai Metal Product Co., Ltd. 氧化锆氧化钇弥散强化钯金合金及其生产方法
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
US8415867B2 (en) 2009-01-23 2013-04-09 Ngk Spark Plug Co., Ltd. Spark plug
EP2554690B1 (en) * 2010-04-02 2019-05-22 Ngk Spark Plug Co., Ltd. Spark plug
DE102014210984A1 (de) * 2014-06-10 2015-12-17 Robert Bosch Gmbh Zündkerzenelektrode, Verfahren zu deren Herstellung und Zündkerze
EP3971311B1 (de) * 2020-09-17 2022-07-06 Heraeus Deutschland GmbH & Co. KG Verbesserte, dispersionsgehärtete edelmetalllegierung
EP3978884B1 (de) * 2020-10-02 2024-05-29 Heraeus Precious Metals GmbH & Co. KG Draht mit platin-zusammensetzung zur kontaktierung von temperatursensoren

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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
CN100379108C (zh) * 2001-03-28 2008-04-02 日本特殊陶业株式会社 火花塞

Also Published As

Publication number Publication date
ES2326042T3 (es) 2009-09-29
ATE428812T1 (de) 2009-05-15
CY1109237T1 (el) 2014-07-02
US7736752B2 (en) 2010-06-15
DK1917370T3 (da) 2009-08-17
DE502006003473D1 (de) 2009-05-28
WO2007019990A1 (de) 2007-02-22
EP1917370A1 (de) 2008-05-07
JP2009504917A (ja) 2009-02-05
PL1917370T3 (pl) 2009-09-30
US20080295925A1 (en) 2008-12-04
JP5294859B2 (ja) 2013-09-18
SI1917370T1 (sl) 2009-10-31
PT1917370E (pt) 2009-07-20

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