EP1722901A1 - Verfahren zur plasmareinigung eines bauteils - Google Patents
Verfahren zur plasmareinigung eines bauteilsInfo
- Publication number
- EP1722901A1 EP1722901A1 EP05701389A EP05701389A EP1722901A1 EP 1722901 A1 EP1722901 A1 EP 1722901A1 EP 05701389 A EP05701389 A EP 05701389A EP 05701389 A EP05701389 A EP 05701389A EP 1722901 A1 EP1722901 A1 EP 1722901A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- crack
- plasma
- chamber
- turbine
- 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
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004140 cleaning Methods 0.000 title claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 claims description 20
- 230000000977 initiatory effect Effects 0.000 claims 2
- 238000000926 separation method Methods 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 239000013078 crystal Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229910000601 superalloy Inorganic materials 0.000 description 3
- 239000012720 thermal barrier coating Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000009419 refurbishment Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000191291 Abies alba Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
Definitions
- the invention relates to a method for plasma cleaning a component according to claim 1.
- the contaminants can be dust particles, oil or grease films or also corrosion products on the surface of the component.
- FIC fluoride ion cleaning
- hydrogen annealing hydrogen annealing
- salt bath cleaning salt bath cleaning
- Plasma-assisted vacuum etching processes of components within known PVD or CVD coating processes immediately prior to vapor deposition are known.
- the basic principle of this surface treatment is the atomization or sputtering of adhering impurities and the upper atomic layers of the material to be removed into particles of an atomic size by bombardment with inert gas ions.
- the very finely atomized contamination has virtually passed into the gas phase and can be extracted.
- Such plasmas can be achieved by coupling suitable electrode arrangements with high-voltage high-frequency generators. However, these methods are only used for cleaning flat surfaces.
- EP 0 313 855 A2 discloses a method for generating a gas plasma, in which the voltage is controlled to a certain value.
- EP 0 740 989 A2 discloses a method for cleaning a vulcanizing mold, in which a plasma stream is generated.
- the problem is solved by a method for
- FIG. 3 a turbine blade
- FIG. 4 a combustion chamber
- FIG. 5 a gas turbine.
- FIG. 1 shows an exemplary device 25 for carrying out the method according to the invention. It consists of a chamber 13 in which a vacuum p prevails. The vacuum p is generated by a pump 16 which is connected to the chamber 13. A component 1 is present in the chamber 13, which has a crack 4 starting from a surface 22. Likewise, an electrode 10 is arranged above the surface 22 of a component 1 in order to initiate and maintain a plasma 7.
- This electrode 10 is at a certain distance d from the surface 22 of the component 1.
- a reactive gas 31 can be present in the chamber 13, which reacts, for example, with a corrosion product in the crack 4 and thus promotes cleaning of the crack 4.
- the component 1 can be metallic or ceramic.
- component 1 is an iron, cobalt or nickel-based superalloy which is used, for example, to produce a turbine blade 12, 130 (FIGS. 3, 5) or combustion chamber lining 155 (FIG. 4) of a turbine 100 (FIG. 5) ,
- Other components of a gas or steam turbine can be cleaned with this method.
- Cracks 4 in component 1 may already be present directly after manufacture or have formed after component 1 has been used in operation. Such worn components 1, 120, 130, 155 are often refurbished (refurbishment). 22 corrosion products are removed from the surface. Corrosion products in crack 4 are more difficult to remove.
- the crack 4 can be welded or soldered, since the solder can adhere very well to a cleaned surface.
- FIG. 2 shows a further device 25 ⁇ with which the inventive method can be carried out.
- the device 25 ⁇ has a control unit 19 which regulates the pressure p in the chamber 13. Since the condition “distance times pressure equals constant” applies to the maintenance of a plasma 7, the pressure p can also be varied in order to initiate and maintain a plasma 7 in the crack 4 at a fixed distance d between the electrode 10 and the surface 22 , For example, by steadily lowering the pressure p, the plasma 7 moves ever lower to the crack tip 34 of the crack 4.
- a reactive gas 31 can be present in the chamber 13, which reacts, for example, with a corrosion product in the crack 4 and thus promotes cleaning of the crack 4.
- Another possibility is to simultaneously vary the pressure and distance so that the plasma 7 is maintained, but the condition for maintaining a plasma 7 (distance times pressure equal constant) is maintained.
- the distance d and the pressure p can be varied simultaneously or alternately.
- An inert gas may be present in chamber 13 (Ar, H 2 , N 2 ).
- FIG. 3 shows a blade 120, 130 in a perspective view, which extends along a longitudinal axis 121.
- the blade 120 can be a rotor blade 120 or a guide blade 130 of a turbomachine for generating plasma.
- the turbomachine can be a gas turbine of an aircraft or a power plant for generating electricity, a steam turbine or a compressor.
- the blade 120, 130 has, along the longitudinal axis 121, successively a fastening region 400, an adjacent blade platform 403 and an airfoil 406.
- As a guide vane 130, the vane can on its
- Blade tip 415 have another platform (not shown).
- a blade root 183 is formed in the fastening area 400 and is used to fasten the moving blades 120, 130 to a shaft or a disk (not shown).
- the blade root 183 is designed, for example, as a hammer head.
- the blade 120, 130 points for a medium attached to the
- Airfoil 406 flows past, a leading edge 409 and a trailing edge 412.
- the blade 120, 130 can be manufactured by a casting process, also by means of directional solidification, by a forging process, by a milling process or combinations thereof.
- Workpieces with a single-crystal structure or structures are used as components for machines that are exposed to high mechanical, thermal and / or chemical loads during operation.
- Such single-crystal workpieces are manufactured e.g. by directional solidification from the melt. These are casting processes in which the liquid metallic alloy forms a single-crystal structure, i.e. to the single-crystalline workpiece, or solidified in a directed manner.
- Dendritic crystals are aligned along the heat flow and either form a stem crystalline Grain structure (columnar, ie grains that run along the entire length of the workpiece and here, according to common usage, are referred to as directionally solidified) or a single-crystal structure, ie the entire workpiece consists of a single crystal.
- a stem crystalline Grain structure columnumnar, ie grains that run along the entire length of the workpiece and here, according to common usage, are referred to as directionally solidified
- a single-crystal structure ie the entire workpiece consists of a single crystal.
- directionally solidified structures If there is general talk of directionally solidified structures, this means both single crystals which have no grain boundaries or at most small-angle grain boundaries, and stem crystal structures which probably have grain boundaries running in the longitudinal direction but no transverse grain boundaries. These second-mentioned crystalline structures are also referred to as directionally solidified structures.
- Refurbishment means that components 120, 130 may need to be cleaned of protective layers after their use (e.g. by sandblasting). The corrosion and / or oxidation layers or products are then removed. If necessary, cracks in component 120, 130 are also repaired. The components 120, 130 are then recoated and the components 120, 130 are used again.
- the blade 120, 130 can be hollow or solid. When the blade 120, 130 is to be cooled, it is hollow and may also have film cooling holes (not shown). To protect against corrosion, the blade 120, 130, for example, has corresponding mostly metallic coatings and, as protection against heat, usually also has a ceramic coating.
- FIG. 4 shows a combustion chamber 110 of a gas turbine.
- the combustion chamber 110 is configured, for example, as a so-called annular combustion chamber, in which a plurality of burners 102 arranged in the circumferential direction around the turbine shaft 103 open into a common combustion chamber space.
- the combustion chamber 110 is configured in its entirety as an annular structure which is positioned around the turbine shaft 103.
- the combustion chamber 110 is designed for a comparatively high temperature of the working medium M of approximately 1000 ° C. to 1600 ° C.
- the combustion chamber wall 153 is provided on its side facing the working medium M with an inner lining formed from heat shield elements 155.
- Each heat shield element 155 is particularly heat-resistant on the working medium side
- Protective layer equipped or made of high temperature resistant material. Due to the high temperatures inside the combustion chamber 110, a cooling system is also provided for the heat shield elements 155 or for their holding elements.
- the materials of the combustion chamber wall and their coatings can be similar to the turbine blades.
- the combustion chamber 110 is designed in particular for the detection of losses of the heat shield elements 155. Is to A number of temperature sensors 158 are positioned between the combustion chamber wall 153 and the heat shield elements 155.
- FIG. 5 shows an example of a gas turbine 100 in a partial longitudinal section.
- the gas turbine 100 has on the inside a rotor 103 which is rotatably mounted about an axis of rotation 102 and is also referred to as a turbine rotor.
- the annular combustion chamber 106 communicates with an annular hot gas duct 111, for example.
- the guide vanes 130 are fastened to an inner housing 138 of a stator 143, whereas the rotor blades 120 of a row 125 are attached to the rotor 103, for example by means of a turbine disk 133.
- a generator or a work machine (not shown) is coupled to the rotor 103.
- the compressor 105 draws in and compresses air 135 through the intake housing 104.
- the compressed air provided at the turbine end of the compressor 105 is led to the burners 107 and mixed there with a fuel.
- the mixture is then burned in the combustion chamber 110 to form the working medium 113.
- Working medium 113 along the hot gas channel 111 past the guide vanes 130 and the rotor blades 120.
- the working medium 113 relaxes in a pulse-transmitting manner on the rotor blades 120, so that the rotor blades 120 drive the rotor 103 and the rotor coupled to it.
- the components exposed to the hot working medium 113 are subject to thermal loads during the operation of the gas turbine 100.
- Rotary blades 120 of the first turbine stage 112 are subjected to the greatest thermal stress in addition to the heat shield bricks lining the annular combustion chamber 106. In order to withstand the temperatures prevailing there, they can be cooled using a coolant.
- substrates of the components can have a directional structure, i.e. they are single-crystal (SX structure) or only have longitudinal grains (DS structure). As material for the components, especially for the
- Turbine blades 120, 130 and components of combustion chamber 110 for example, iron, nickel or cobalt-based super alloys are used.
- Such superalloys are known, for example, from EP 1204776, EP 1306454, EP 1319729, WO 99/67435 or WO 00/44949; these scriptures are part of the revelation.
- the blades 120, 130 can also counter coatings
- M is at least one element from the group iron (Fe), cobalt (Co), nickel (Ni), X is an active element and stands for yttrium (Y) and / or silicon and / or at least one element of the rare earths ) and have heat through a thermal barrier coating.
- the thermal barrier coating is, for example, Zr0 2 , Y 2 0-Zr0 2 , ie it is not, partially or completely stabilized by yttrium oxide and / or calcium oxide and / or
- EB-PVD electron beam evaporation
- the guide blade 130 has a guide blade foot (not shown here) facing the inner housing 138 of the turbine 108 and a guide blade head opposite the guide blade foot.
- the guide vane head faces the rotor 103 and is fixed to a fastening ring 140 of the stator 143.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05701389A EP1722901B1 (de) | 2004-03-02 | 2005-02-09 | Verfahren zur plasmareinigung eines bauteils |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04004892A EP1570921A1 (de) | 2004-03-02 | 2004-03-02 | Verfahren zur Plasmareinigung eines Bauteils |
EP05701389A EP1722901B1 (de) | 2004-03-02 | 2005-02-09 | Verfahren zur plasmareinigung eines bauteils |
PCT/EP2005/001301 WO2005084830A1 (de) | 2004-03-02 | 2005-02-09 | Verfahren zur plasmareinigung eines bauteils |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1722901A1 true EP1722901A1 (de) | 2006-11-22 |
EP1722901B1 EP1722901B1 (de) | 2009-04-22 |
Family
ID=34745985
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04004892A Withdrawn EP1570921A1 (de) | 2004-03-02 | 2004-03-02 | Verfahren zur Plasmareinigung eines Bauteils |
EP05701389A Not-in-force EP1722901B1 (de) | 2004-03-02 | 2005-02-09 | Verfahren zur plasmareinigung eines bauteils |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04004892A Withdrawn EP1570921A1 (de) | 2004-03-02 | 2004-03-02 | Verfahren zur Plasmareinigung eines Bauteils |
Country Status (5)
Country | Link |
---|---|
US (1) | US7513955B2 (de) |
EP (2) | EP1570921A1 (de) |
CN (1) | CN100586586C (de) |
DE (1) | DE502005007139D1 (de) |
WO (1) | WO2005084830A1 (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7544254B2 (en) * | 2006-12-14 | 2009-06-09 | Varian Semiconductor Equipment Associates, Inc. | System and method for cleaning an ion implanter |
DE102008019892A1 (de) * | 2008-04-21 | 2009-10-29 | Mtu Aero Engines Gmbh | Verfahren zum Reinigen eines Flugtriebwerks |
DE102008058913A1 (de) | 2008-11-25 | 2010-05-27 | Rolls-Royce Deutschland Ltd & Co Kg | Verfahren zur Herstellung hybrider Bauteile für Fluggasturbinen |
FR2994538B1 (fr) * | 2012-08-14 | 2014-07-25 | Snecma | Outillage pour le dessablage d'une turbomachine |
DE102013107400B4 (de) * | 2013-07-12 | 2017-08-10 | Ks Huayu Alutech Gmbh | Verfahren zur Entfernung des Oversprays eines thermischen Spritzbrenners |
US11668198B2 (en) | 2018-08-03 | 2023-06-06 | Raytheon Technologies Corporation | Fiber-reinforced self-healing environmental barrier coating |
US10934220B2 (en) * | 2018-08-16 | 2021-03-02 | Raytheon Technologies Corporation | Chemical and topological surface modification to enhance coating adhesion and compatibility |
US11535571B2 (en) | 2018-08-16 | 2022-12-27 | Raytheon Technologies Corporation | Environmental barrier coating for enhanced resistance to attack by molten silicate deposits |
US11505506B2 (en) | 2018-08-16 | 2022-11-22 | Raytheon Technologies Corporation | Self-healing environmental barrier coating |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4028787A (en) * | 1975-09-15 | 1977-06-14 | Cretella Salvatore | Refurbished turbine vanes and method of refurbishment thereof |
US4098450A (en) * | 1977-03-17 | 1978-07-04 | General Electric Company | Superalloy article cleaning and repair method |
US4853081A (en) * | 1987-10-30 | 1989-08-01 | Ibm Corporation | Process for removing contaminant |
US5769953A (en) * | 1995-05-01 | 1998-06-23 | Bridgestone Corporation | Plasma and heating method of cleaning vulcanizing mold for ashing residue |
JP2002527628A (ja) | 1998-10-21 | 2002-08-27 | シーメンス アクチエンゲゼルシヤフト | 製品の浄化方法と被覆方法およびそのための装置 |
US7451774B2 (en) * | 2000-06-26 | 2008-11-18 | Applied Materials, Inc. | Method and apparatus for wafer cleaning |
FR2836157B1 (fr) * | 2002-02-19 | 2004-04-09 | Usinor | Procede de nettoyage de la surface d'un materiau enduit d'une susbstance organique, generateur et dispositif de mise en oeuvre |
US20050035085A1 (en) * | 2003-08-13 | 2005-02-17 | Stowell William Randolph | Apparatus and method for reducing metal oxides on superalloy articles |
-
2004
- 2004-03-02 EP EP04004892A patent/EP1570921A1/de not_active Withdrawn
-
2005
- 2005-02-09 DE DE502005007139T patent/DE502005007139D1/de active Active
- 2005-02-09 CN CN200580006606A patent/CN100586586C/zh not_active Expired - Fee Related
- 2005-02-09 EP EP05701389A patent/EP1722901B1/de not_active Not-in-force
- 2005-02-09 US US10/591,512 patent/US7513955B2/en not_active Expired - Fee Related
- 2005-02-09 WO PCT/EP2005/001301 patent/WO2005084830A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO2005084830A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1722901B1 (de) | 2009-04-22 |
CN1946489A (zh) | 2007-04-11 |
WO2005084830A1 (de) | 2005-09-15 |
EP1570921A1 (de) | 2005-09-07 |
DE502005007139D1 (de) | 2009-06-04 |
US20070215174A1 (en) | 2007-09-20 |
US7513955B2 (en) | 2009-04-07 |
CN100586586C (zh) | 2010-02-03 |
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