EP1481574B1 - Procede de fabrication d'un element electrode pour chalumeau a plasma - Google Patents
Procede de fabrication d'un element electrode pour chalumeau a plasma Download PDFInfo
- Publication number
- EP1481574B1 EP1481574B1 EP03729808A EP03729808A EP1481574B1 EP 1481574 B1 EP1481574 B1 EP 1481574B1 EP 03729808 A EP03729808 A EP 03729808A EP 03729808 A EP03729808 A EP 03729808A EP 1481574 B1 EP1481574 B1 EP 1481574B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- core
- metal
- work function
- alloy
- electrode
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 25
- 239000011162 core material Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 23
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052735 hafnium Inorganic materials 0.000 claims description 18
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 9
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 229910001029 Hf alloy Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000009694 cold isostatic pressing Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000006104 solid solution Substances 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 26
- 239000010949 copper Substances 0.000 description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/34—Details, e.g. electrodes, nozzles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/32—Plasma torches using an arc
- H05H1/34—Details, e.g. electrodes, nozzles
- H05H1/3442—Cathodes with inserted tip
Definitions
- the invention relates to a manufacturing method for electrode elements for plasma torches.
- Such an electrode element is particularly suitable for plasma cutting, in which oxygen is used as plasma gas.
- the high thermal stress through temperatures up to 50,000 Kelvin requires a suitable design and a suitable selection of the materials used for such an electrode.
- electrodes consisting essentially of hafnium, having a melting temperature in the range of 2220 ° C used.
- Hafnium has a low work function, unlike many other electrically conductive metals, making it particularly suitable for use.
- pin-shaped hafnium electrodes are used with a copper mount and thereby exploited the high thermal and electrical conductivity of the copper.
- the prior art uses silver or a silver alloy.
- Silver also has good thermal and electrical conductivities and higher work function.
- oxide formation is lower with silver over copper at higher temperatures.
- EP 0 437 915 A2 A similar solution is also out EP 0 437 915 A2 known.
- a cathode-forming insert made of a metal or a metal alloy with lower work function of a sleeve of a metal or metal alloy with higher work function present, which are metallurgically connected to each other.
- An analogous electrode is also made EP 1 272 013 A2 known.
- an element is encased as a cathode of a metal or metal alloy with low work function of a metal (Ag, Au, Cu, Al) or a metal alloy with a higher work function sleeve-shaped.
- a cylindrical receptacle for the element can be formed in the sleeve-shaped element by drilling or by extrusion.
- EP 0 334 981 A1 is a material for electrodes disclosed.
- the electrode element produced according to the invention for the plasma torch in question has at least one core of a metal or a metal alloy with a smaller work function than a metal or a metal alloy, from which / a shell part enclosing the at least one core is formed, wherein the one or more Also, several core (s) form the actual electrode connected as a cathode.
- a boundary layer formed in graded form which is formed from mixed crystals of the respective metals or metal alloys.
- an intermediate layer between the core surface and the cladding part material is formed from a further metal or metal alloy having a larger work function than that of the core material, wherein the intermediate layer in the direction of core and cladding part in each case a graded transition in Form forms of appropriately trained boundary layers.
- the core hafnium or a hafnium alloy can be used, wherein the proportion of alloy components should be kept relatively small.
- hafnium or its alloys but also tungsten, zirconium or tantalum or alloys of these elements can be used as core materials.
- a preferred material for the shell part is copper or a copper alloy.
- the intermediate layer can again be formed from silver or a silver alloy.
- each forming graded transitions of the different materials are in the known from the prior art solutions, such as in the in EP 0 980 197 A2 described does not exist, because this is constructive and manufacturing conditionally not possible.
- the electrode elements according to the invention can be produced simply and inexpensively by a shaping and joining method utilizing compressive forces (pressing forces), wherein the corresponding boundary layers with the graded transitions can be formed without additional technological process steps.
- the production takes place by extrusion.
- the shell part and / or an intermediate layer corresponding rod, wire or sleeve-shaped elements of the respective metals or metal alloys can be used, which then by extrusion to form an electrode element according to the invention be deformed.
- the respective metal or metal alloy in powder form for these elements.
- the use of powdery, for example silver is particularly favorable.
- the space between a sleeve-shaped copper part and at least one core forming rod or wire-shaped element can be filled with a silver powder and the corresponding intermediate layer can form with a respective graded transition towards the core surface and in the direction of the shell part due to the compressive forces acting during extrusion ,
- a mixing zone which can be achieved by the individual grains of the powder starting material, of the respective two metals or metal alloys is formed, which is homogeneous over the entire available area.
- the core and shell part also corresponding powder.
- the starting powders used can then by means of a pressing process, preferably by cold isostatic pressing individually or successively successively to precursors, which ensure sufficient strength for the subsequent extrusion process, and subsequently formed by extrusion molding an inventive electrode element.
- the one or more core (s) can be used as a precursor rod-shaped elements having a circular cross-section.
- elements whose cross sections are cross-shaped or star-shaped can also be used to form the cores forming the actual electrodes.
- Such an element may then have three or more webs, which are each aligned at equal angular intervals to each other, and it is thereby achievable an enlargement of the respective transitional surfaces with the associated low electrical and thermal contact resistance between the core and shell part or intermediate layer.
- a core can also be formed from a plurality of wire-shaped elements twisted together, similar to frequently used in electrical lines strands.
- a core thus formed by twisting wire-shaped elements also increases the contact area and at the same time the advantageous gradation effect.
- an electrode element according to the invention it is advantageous to arrange them discretely and equidistant from one another, wherein they are embedded in the sheath part material, optionally with the interposition of an intermediate layer.
- a Preheating Before extruding a Preheating be carried out to a temperature of at least 400 ° C, in particular to reduce the stress of the extrusion die.
- a preheating also has a favorable effect on the formation of mixed crystals or diffusion processes, which can thus take place with great certainty in the simultaneously acting relatively high pressure forces during the extrusion.
- An inventive electrode element has by the intimate bond with the graded transitions of the various metals or metal alloys of the individual elements low thermal and electrical contact resistance, so that the problem of current corrosion counteracted and the life can be significantly increased. Consequently, not only the manufacturing cost of the electrode elements per se, but also the operating costs of a suitably equipped plasma torch at the end user are significantly reduced.
- the electrode elements produced by the method according to the invention in which intermediate layers of silver or silver alloys are used, can be produced more cost-effectively, since such intermediate layers can be formed with significantly lower layer thickness, so that the costly use of silver can be reduced accordingly.
- a sleeve-shaped copper element can be used for the formation of a jacket part.
- at least one rod-shaped element made of, for example, hafnium can be introduced over the entire length of the copper sleeve, into the interior of which.
- such a copper sleeve has an outside diameter of, for example 12 mm and the free cross-section inside such a copper sleeve have a diameter of 1.5 mm.
- An electrode element thus obtained must then be used only in a corresponding plasma torch, wherein such a plasma torch can also be formed so that a certain, arranged in the interior of a plasma tor part of such an electrode element can be flowed around directly by a cooling medium for dissipating heat.
- hafnium wires can be introduced into such a copper sleeve, wherein Kupferhülseninnen penmesser and the largest extent of such Kernvoriatas should be dimensioned so that a fillable with a silver powder or a silver powder alloy gap remains.
- Such a silver powder forming an intermediate layer should as far as possible also be used if a core with a non-rotationally symmetrical cross-sectional shape or a sleeve-shaped core is to be formed.
- a rod-shaped element made of hafnium on its outer surface in the direction of the jacket part material with a layer formed essentially of silver powder.
- a powder can for example be applied in the form of a suspension and For example, solidified by a pressing process on the surface of the rod-shaped Hafniumimplantations or subjected to sintering.
- the suspension containing the silver powder can then also contain an organic binder which can be expelled thermally during sintering.
- a rod-shaped element provided with such a silver layer can then be reinserted into a sleeve-shaped copper element and an electrode element according to the invention produced by extrusion molding.
- the electrode element according to the invention can also be further developed in that by forming a corresponding contour, wherein preferably an external thread can be selected to be able to connect this with a sleeve-shaped element.
- a sleeve-shaped element which is preferably made of copper, can then be reused several times and so it is only an exchange of the correspondingly smaller dimensioned electrode element in more or less large intervals required.
- the electrode element is simply screwed in or out with the thread formed on its outer circumferential surface, as an outline shape, into a sleeve-shaped element.
- the element according to the invention can also be designed and manufactured such that a cavity open on one side has been formed inside the shell part.
- This cavity can be connected to the filling system of a plasma torch be placed in communication, so that the cooling medium, preferably water for heat dissipation can get directly into this cavity.
- the formation of such a cavity can be formed by a scrub profilef doublpressen.
- This process can also be used to avoid machining.
- the backward extrusion is a subsequent processing step on an electrode element whose fabrication has been previously described.
- an electrode element is prepared as a precursor, which is shorter in length than the finished electrode element with the cavity and in its outer diameter is larger than this.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Arc Welding In General (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Plasma Technology (AREA)
Claims (15)
- Procédé de fabrication d'un élément d'électrode pour un chalumeau à plasma comportant une partie en forme de douille formant une partie de gainage, constituée d'un métal ou d'un alliage de métal avec un travail de sortie élevé et une conductibilité électrique thermique élevée, dans lequel au moins un élément de coeur formant l'électrode en fait connectée en tant que cathode, constitué d'un métal ou d'un alliage de métal est mis en place avec un travail de sortie inférieur,
caractérisé en ce que l'élément d'électrode est fabriqué par extrusion après un préchauffage à au moins 400 °C. - Procédé selon la revendication 1,
caractérisé en ce que, avant l'extrusion, la cavité entre la partie en forme de douille et l'élément de coeur est remplie pour former une couche intermédiaire avec un autre métal pulvérulent ou un alliage de métal ayant un travail de sortie supérieur à celui du matériau de coeur et une conductibilité thermique et électrique supérieure à celle du matériau de coeur. - Procédé selon la revendication 1 ou 2, caractérisé en ce que, pour former un coeur, plusieurs éléments filiformes sont torsadés ensemble.
- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la cavité d'un élément de coeur en forme de douille est remplie, avant l'extrusion, avec une poudre d'un métal ou d'un alliage de métal ayant un travail de sortie supérieur à celui du matériau de coeur.
- Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la partie de gainage, le coeur et/ou la couche intermédiaire constitués d'une poudre forment, au moyen d'un procédé de pressage, chacun un produit préliminaire ou un produit préliminaire commun, et sont fabriqués à partir d'un ou plusieurs produits préliminaires par extrusion de l'élément d'électrode.
- Procédé selon la revendication 5, caractérisé en ce que le/les produit(s) préliminaire(s) est/sont fabriqué(s) par pressage isostatique à froid.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que sur la surface de gainage externe de la partie de gainage, un contour est formé pour une connexion à forme finale avec une partie en cuivre en forme de douille.
- Procédé selon l'une quelconque des revendications 1 à 7,
caractérisé en ce que, à l'intérieur de la partie de gainage, une cavité ouverte d'un côté est formée par extrusion en arrière. - Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la couche frontière entre la surface de coeur et la partie de gainage est formée avec des gradations de cristaux mixtes des deux métaux ou alliages de métaux.
- Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que une couche intermédiaire de la surface de coeur et de la partie de gainage, constituée d'un autre métal ou alliage de métal avec un travail de sortie supérieur formant le matériau de coeur, est formée de couches frontières ayant des transitions graduées.
- Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que de l'hafnium ou un alliage d'hafnium est utilisé pour la fabrication du coeur.
- Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que du tungstène, du zirconium, du tantale ou un alliage de ces éléments est utilisé pour la fabrication du coeur.
- Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que de l'argent ou un alliage d'argent est utilisé pour la couche intermédiaire.
- Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le coeur est fabriqué avec une section transversale en forme de couronne circulaire, en forme d'étoile, ou en forme de croix.
- Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce que l'électrode est fabriquée avec plusieurs coeurs agencés séparément.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10210421A DE10210421B4 (de) | 2002-03-06 | 2002-03-06 | Elektrodenelement für Plasmabrenner sowie Verfahren zur Herstellung |
DE10210421 | 2002-03-06 | ||
PCT/DE2003/000763 WO2003075621A2 (fr) | 2002-03-06 | 2003-03-05 | Element electrode pour chalumeau a plasma et procede de fabrication |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1481574A2 EP1481574A2 (fr) | 2004-12-01 |
EP1481574B1 true EP1481574B1 (fr) | 2008-12-17 |
Family
ID=27771139
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03729808A Expired - Lifetime EP1481574B1 (fr) | 2002-03-06 | 2003-03-05 | Procede de fabrication d'un element electrode pour chalumeau a plasma |
Country Status (6)
Country | Link |
---|---|
US (1) | US7098422B2 (fr) |
EP (1) | EP1481574B1 (fr) |
AT (1) | ATE418258T1 (fr) |
AU (1) | AU2003240381A1 (fr) |
DE (2) | DE10210421B4 (fr) |
WO (1) | WO2003075621A2 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7112759B1 (en) * | 2005-06-07 | 2006-09-26 | The Esab Group, Inc. | Plasma torch with interchangeable electrode systems |
US8101882B2 (en) * | 2005-09-07 | 2012-01-24 | Hypertherm, Inc. | Plasma torch electrode with improved insert configurations |
DE102009058831A1 (de) * | 2009-12-18 | 2011-07-14 | Holma Ag | Elektrode für einen Plasmabrenner |
US9949356B2 (en) | 2012-07-11 | 2018-04-17 | Lincoln Global, Inc. | Electrode for a plasma arc cutting torch |
CN112996208B (zh) * | 2019-12-16 | 2023-07-07 | 新奥科技发展有限公司 | 一种等离子体炬阴极及其制备方法 |
CN113053705B (zh) * | 2021-02-05 | 2022-05-10 | 浙江大学 | 一种耐电弧烧蚀的铪铜复合电极及其制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041711A (en) * | 1985-10-04 | 1991-08-20 | Hobie Holding, Inc. | Spot welding electrode |
JPS63199842A (ja) * | 1987-02-14 | 1988-08-18 | Toho Kinzoku Kk | 電極材料 |
US5004888A (en) * | 1989-12-21 | 1991-04-02 | Westinghouse Electric Corp. | Plasma torch with extended life electrodes |
US5023425A (en) * | 1990-01-17 | 1991-06-11 | Esab Welding Products, Inc. | Electrode for plasma arc torch and method of fabricating same |
JPH07130490A (ja) * | 1993-11-02 | 1995-05-19 | Komatsu Ltd | プラズマトーチ |
US5767478A (en) | 1997-01-02 | 1998-06-16 | American Torch Tip Company | Electrode for plasma arc torch |
US6130399A (en) * | 1998-07-20 | 2000-10-10 | Hypertherm, Inc. | Electrode for a plasma arc torch having an improved insert configuration |
US6020572A (en) * | 1998-08-12 | 2000-02-01 | The Esab Group, Inc. | Electrode for plasma arc torch and method of making same |
US6420673B1 (en) * | 2001-02-20 | 2002-07-16 | The Esab Group, Inc. | Powdered metal emissive elements |
-
2002
- 2002-03-06 DE DE10210421A patent/DE10210421B4/de not_active Expired - Fee Related
-
2003
- 2003-03-05 EP EP03729808A patent/EP1481574B1/fr not_active Expired - Lifetime
- 2003-03-05 US US10/506,696 patent/US7098422B2/en not_active Expired - Fee Related
- 2003-03-05 AT AT03729808T patent/ATE418258T1/de active
- 2003-03-05 DE DE50310929T patent/DE50310929D1/de not_active Expired - Lifetime
- 2003-03-05 AU AU2003240381A patent/AU2003240381A1/en not_active Abandoned
- 2003-03-05 WO PCT/DE2003/000763 patent/WO2003075621A2/fr not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
ATE418258T1 (de) | 2009-01-15 |
US20050161443A1 (en) | 2005-07-28 |
AU2003240381A1 (en) | 2003-09-16 |
DE10210421B4 (de) | 2007-11-22 |
DE10210421A1 (de) | 2003-10-02 |
US7098422B2 (en) | 2006-08-29 |
DE50310929D1 (de) | 2009-01-29 |
WO2003075621A3 (fr) | 2003-11-13 |
EP1481574A2 (fr) | 2004-12-01 |
WO2003075621A2 (fr) | 2003-09-12 |
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