EP1523390A2 - Verfahren zur endkonturnahen herstellung von hochpor sen met allischen formk rpern - Google Patents
Verfahren zur endkonturnahen herstellung von hochpor sen met allischen formk rpernInfo
- Publication number
- EP1523390A2 EP1523390A2 EP03737877A EP03737877A EP1523390A2 EP 1523390 A2 EP1523390 A2 EP 1523390A2 EP 03737877 A EP03737877 A EP 03737877A EP 03737877 A EP03737877 A EP 03737877A EP 1523390 A2 EP1523390 A2 EP 1523390A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- placeholder
- green body
- sintering
- green
- highly porous
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F2003/1042—Sintering only with support for articles to be sintered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the invention relates to a method with which a near-net-shape production of porous, in particular highly porous, components can be achieved.
- high-melting inorganic compounds such as alkali salts and low-melting metals such as Mg, Sn, Pb etc. are also used as placeholder materials.
- Such placeholder materials are removed from the green bodies in a vacuum or under protective gas at temperatures between approx. 600 to 1000 ° C with a high expenditure of energy and time. With these placeholder materials, impurities remaining in the green body cannot be prevented, which are particularly harmful in the case of shaped bodies made of reactive metal powders such as Ti, Al, Fe, Cr, Ni.
- DE 196 38 927 C2 discloses a method for producing highly porous, metallic moldings, in which metal powder and a placeholder are first mixed and then pressed to form a green product. Both uniaxial and isostatic pressing can be used. The placeholder is driven out thermally and then the green body sintered. If the powder-placeholder mixture is stabilized by a binder, it is in principle possible to implement relatively complex component geometries directly using multi-axial pressing. However, the production of a suitable press tool is complex and expensive. For small series in particular, it is therefore advantageous to first manufacture semi-finished products with a universal geometry (eg cylinders or plates) and then bring them to the desired final contour by means of subsequent mechanical processing.
- a universal geometry eg cylinders or plates
- the final shaping of highly porous moldings takes place only after sintering using conventional mechanical methods such as turning, milling, drilling or grinding.
- the disadvantage of this subsequent processing of the already sintered semi-finished product is that it is associated with local material deformation.
- the plastic deformation regularly causes the pores to smear.
- the desired open porosity of the molding is regularly lost, especially in the surface area. This adversely affects the functional properties of the molded body.
- the workpiece should only be clamped and processed with caution, since it is not very pressure-stable.
- the uneven surface of the porous molded body also causes relatively high tool wear. Task and solution
- the object of the invention is to provide a simple method for producing a highly porous, metallic molded body which in particular has a highly complicated geometry and which does not have the disadvantages mentioned above, e.g. B. has impaired porosity on the surface.
- the invention relates to a method for producing highly porous metallic moldings.
- the process comprises the following process steps.
- a metal powder used as the starting material is mixed with a placeholder.
- the metal powder can be, for example, titanium and its alloys, iron and its alloys, nickel and its alloys, copper, bronze, molybdenum, niobium, tantalum and tungsten.
- Suitable placeholders are, for example, carbamide CH 4 N 2 0 (H 2 N-CO-NH 2 ), biuret C 2 H 5 N 3 0 2 , melamine C 3 H 6 N 6 , melamine resin, ammonium carbonate (NH 4 ) C0 3 H 2 0 and ammonium bicarbonate NH 4 HC0 3 , which are residue-free at temperatures up to max. 300 ° C can be removed from the green body.
- Ammonium bicarbonate has been found to be particularly advantageous as a placeholder material, which can be expelled in air at approximately 65 ° C.
- the grain size, ie the particle size and the particle shape of the placeholder material determine the porosity that forms in the shaped body.
- the diameter of the placeholder material is 50 ⁇ m to 2 mm.
- a green body in particular a green body with a simple geometry, is pressed from the mixture.
- This can be a cylinder or a plate, for example.
- Multi-axial pressing and cold isostatic pressing can be used as the pressing process.
- Multi-axial pressing leads to dimensionally stable semi-finished products with defined outer contours.
- the wall friction during demolding causes the formation of a so-called press skin, which is formed from plastically deformed, metallic powder particles. This can be removed by mechanical processing before sintering, provided there is no further green processing.
- the wall friction limits the length to diameter ratio to 2 to 1. Above this value, too large
- the processing at the stage of the greens, in which the placeholder is still present, has the advantage that the workpiece is very easy to process and the porosity is not impaired. Tool wear is therefore kept to a minimum. Even highly complicated shapes are possible with this process.
- the existing placeholder makes the workpiece to be machined sufficiently pressure-stable to be able to clamp it for the subsequent mechanical machining.
- the placeholder material is thermally removed from the green body in air or under vacuum or under protective gas.
- the atmosphere depends on the chosen placeholder material. For example, an air atmosphere above 65 ° C is sufficient to be ammonium bicarbonate
- the green body is then sintered into the shaped body.
- the mechanical processing before sintering advantageously enables simple, near-net-shape production even for complicated geometries of the material to be produced
- This process is not only limited to the production of molded articles with a uniform porosity, but it can also be used to produce molded articles with a different, e.g. B. produce graded porosity.
- Figure 1 possible embodiments of the semi-finished products, which were produced by multi-axial pressing and by cold isostatic pressing.
- Figure 2 various model geometries, which were made of stainless steel 1.4404 (316L) according to the inventive method.
- Figure 3 Representation of the macroporosity that is set by the placeholder material and the microporosity that occurs within the sintering webs.
- the typical process sequence of the process according to the invention is structured as follows.
- a semi-finished product is produced based on DE 196 38 927.
- a metal powder in particular the stainless steel 1.4404 (316L) or titanium, is mixed with a placeholder, in particular ammonium bicarbonate, and pressed uniaxially or cold isostatically.
- a placeholder in particular ammonium bicarbonate
- FIG. 1 shows possible embodiments of the semi-finished products which were produced by multi-axial pressing and by cold isostatic pressing.
- the placeholder advantageously increases the green strength of the semi-finished products and thus has a favorable effect on the machinability.
- Another advantage of machining is the low cutting force and, accordingly, the low tool wear. Smearing of the pores is also avoided.
- the removal of the placeholder and the sintering can be carried out conventionally on a planar sintering sub- ge made of ceramic or alternatively in a bed of ceramic balls.
- the parameters for removing the placeholder can be selected based on DE 196 38 927 C2.
- the placeholders ammonium carbonate and ammonium bicarbonate are removed in air.
- the sintering in a ball bed has the advantage that the contact surfaces to the component are small, thus preventing the component from adhering to the ceramic balls.
- the ball bed can easily compensate for the sintering shrinkage by reorienting the balls, so that there is even contact with the sintered layer during the entire sintering process. This avoids warping of the components during sintering.
- the moldings can then be trovalized to improve the surface quality.
- FIG. 2 shows various model geometries which were produced from the stainless steel 1.4404 (316L) according to the process sequence according to the invention and described below.
- a water-poor powder (grain fraction ⁇ 50 ⁇ m) was used as the starting material.
- the steel powder was mixed with the placeholder ammonium bicarbonate (grain fraction 355 to 500 ⁇ m) in the ratio of steel powder to ammonium bicarbonate 45 to 55 (in% by volume). This corresponds to a ratio of steel powder to placeholder of 80.5 to 19.5 in% by weight.
- the mixture became uniaxial with a press pressure of 425
- the placeholder ammonium bicarbonate was removed in air at a temperature of 105 ° C. Although the decomposition of the placeholder already started at 65 ° C, the higher temperature was chosen in order to be able to remove the decomposition product water in the gaseous state.
- the sintering was carried out at 1120 ° C for 2 hours under an argon atmosphere.
- the model geometries showed a shrinkage of approx. 4%.
- the final porosity of the components was around 60%.
- the microporosity results from incomplete sintering of the metal powder particles. To reduce the microporosity, the use of finer starting powder or sintering at higher temperatures is recommended.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
- Filtering Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Image Analysis (AREA)
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10224671A DE10224671C1 (de) | 2002-06-03 | 2002-06-03 | Verfahren zur endkonturnahen Herstellung von hochporösen metallischen Formkörpern |
| DE10224671 | 2002-06-03 | ||
| PCT/DE2003/001484 WO2003101647A2 (de) | 2002-06-03 | 2003-05-09 | Verfahren zur endkonturnahen herstellung von hochporösen metallischen formkörpern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1523390A2 true EP1523390A2 (de) | 2005-04-20 |
| EP1523390B1 EP1523390B1 (de) | 2008-06-25 |
Family
ID=28051332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03737877A Expired - Lifetime EP1523390B1 (de) | 2002-06-03 | 2003-05-09 | Verfahren zur endkonturnahen herstellung von hochporösen met allischen formkörpern |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7147819B2 (de) |
| EP (1) | EP1523390B1 (de) |
| JP (1) | JP4546238B2 (de) |
| CN (1) | CN1863630B (de) |
| AT (1) | ATE399070T1 (de) |
| AU (1) | AU2003245820B2 (de) |
| BR (1) | BR0311587B1 (de) |
| CA (1) | CA2488364C (de) |
| DE (2) | DE10224671C1 (de) |
| ES (1) | ES2307948T3 (de) |
| PL (1) | PL205839B1 (de) |
| WO (1) | WO2003101647A2 (de) |
| ZA (2) | ZA200410364B (de) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6558426B1 (en) | 2000-11-28 | 2003-05-06 | Medidea, Llc | Multiple-cam, posterior-stabilized knee prosthesis |
| US8123814B2 (en) | 2001-02-23 | 2012-02-28 | Biomet Manufacturing Corp. | Method and appartus for acetabular reconstruction |
| US7597715B2 (en) | 2005-04-21 | 2009-10-06 | Biomet Manufacturing Corp. | Method and apparatus for use of porous implants |
| US8066778B2 (en) | 2005-04-21 | 2011-11-29 | Biomet Manufacturing Corp. | Porous metal cup with cobalt bearing surface |
| US8021432B2 (en) * | 2005-12-05 | 2011-09-20 | Biomet Manufacturing Corp. | Apparatus for use of porous implants |
| US8266780B2 (en) | 2005-04-21 | 2012-09-18 | Biomet Manufacturing Corp. | Method and apparatus for use of porous implants |
| US8292967B2 (en) | 2005-04-21 | 2012-10-23 | Biomet Manufacturing Corp. | Method and apparatus for use of porous implants |
| DK1896379T3 (da) * | 2005-06-27 | 2010-05-10 | Leuven K U Res & Dev | Fremgangsmåde til fremstilling af sintrede porøse materialer |
| US7635447B2 (en) * | 2006-02-17 | 2009-12-22 | Biomet Manufacturing Corp. | Method and apparatus for forming porous metal implants |
| DE102006036039A1 (de) * | 2006-08-02 | 2008-02-07 | Forschungszentrum Jülich GmbH | Implantate mit poröser Außenschicht sowie Verfahren zur Herstellung derselben |
| WO2008063526A1 (en) * | 2006-11-13 | 2008-05-29 | Howmedica Osteonics Corp. | Preparation of formed orthopedic articles |
| US20080199720A1 (en) * | 2007-02-21 | 2008-08-21 | Depuy Products, Inc. | Porous metal foam structures and methods |
| US8128703B2 (en) | 2007-09-28 | 2012-03-06 | Depuy Products, Inc. | Fixed-bearing knee prosthesis having interchangeable components |
| US8715359B2 (en) | 2009-10-30 | 2014-05-06 | Depuy (Ireland) | Prosthesis for cemented fixation and method for making the prosthesis |
| US8632600B2 (en) | 2007-09-25 | 2014-01-21 | Depuy (Ireland) | Prosthesis with modular extensions |
| US9204967B2 (en) | 2007-09-28 | 2015-12-08 | Depuy (Ireland) | Fixed-bearing knee prosthesis having interchangeable components |
| US8871142B2 (en) | 2008-05-22 | 2014-10-28 | DePuy Synthes Products, LLC | Implants with roughened surfaces |
| DK2130518T3 (da) | 2008-06-03 | 2013-07-29 | Depuy Products Inc | Porøse femorale titanbøsninger |
| ES2455090T3 (es) | 2008-06-03 | 2014-04-14 | Depuy (Ireland) | Manguitos tibiales porosos en titanio |
| US8206451B2 (en) | 2008-06-30 | 2012-06-26 | Depuy Products, Inc. | Posterior stabilized orthopaedic prosthesis |
| US8828086B2 (en) | 2008-06-30 | 2014-09-09 | Depuy (Ireland) | Orthopaedic femoral component having controlled condylar curvature |
| US9168145B2 (en) | 2008-06-30 | 2015-10-27 | Depuy (Ireland) | Posterior stabilized orthopaedic knee prosthesis having controlled condylar curvature |
| US8187335B2 (en) | 2008-06-30 | 2012-05-29 | Depuy Products, Inc. | Posterior stabilized orthopaedic knee prosthesis having controlled condylar curvature |
| US8192498B2 (en) | 2008-06-30 | 2012-06-05 | Depuy Products, Inc. | Posterior cructiate-retaining orthopaedic knee prosthesis having controlled condylar curvature |
| US9119723B2 (en) | 2008-06-30 | 2015-09-01 | Depuy (Ireland) | Posterior stabilized orthopaedic prosthesis assembly |
| US20090326674A1 (en) * | 2008-06-30 | 2009-12-31 | Depuy Products, Inc. | Open Celled Metal Implants With Roughened Surfaces and Method for Roughening Open Celled Metal Implants |
| US8236061B2 (en) | 2008-06-30 | 2012-08-07 | Depuy Products, Inc. | Orthopaedic knee prosthesis having controlled condylar curvature |
| US20100098574A1 (en) | 2008-08-27 | 2010-04-22 | Liu Hengda D | Mixtures For Forming Porous Constructs |
| US8383187B2 (en) | 2009-02-19 | 2013-02-26 | Depuy Products, Inc. | Rough porous constructs |
| US11213397B2 (en) | 2009-05-21 | 2022-01-04 | Depuy Ireland Unlimited Company | Prosthesis with surfaces having different textures and method of making the prosthesis |
| US9101476B2 (en) | 2009-05-21 | 2015-08-11 | Depuy (Ireland) | Prosthesis with surfaces having different textures and method of making the prosthesis |
| EP2314401A1 (de) | 2009-09-09 | 2011-04-27 | DePuy Products, Inc. | Gussformgestaltung und Pulverformverfahren |
| US8383033B2 (en) * | 2009-10-08 | 2013-02-26 | Biomet Manufacturing Corp. | Method of bonding porous metal to metal substrates |
| JP5657275B2 (ja) * | 2009-10-31 | 2015-01-21 | 株式会社Uacj | 多孔質金属及びその製造方法 |
| CN101704103B (zh) * | 2009-12-22 | 2012-12-05 | 元磁新型材料(苏州)有限公司 | 一种用于制造热导管内壁毛细结构的复合铜粉 |
| US9011547B2 (en) | 2010-01-21 | 2015-04-21 | Depuy (Ireland) | Knee prosthesis system |
| WO2011144417A1 (en) * | 2010-05-20 | 2011-11-24 | Nv Bekaert Sa | 3d porous material comprising machined side |
| RU2508962C1 (ru) * | 2012-11-29 | 2014-03-10 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пермский национальный исследовательский политехнический университет" | Способ получения высокопористого ячеистого материала |
| US9949837B2 (en) | 2013-03-07 | 2018-04-24 | Howmedica Osteonics Corp. | Partially porous bone implant keel |
| DE102014110903A1 (de) * | 2014-07-31 | 2016-02-04 | Hoerbiger Antriebstechnik Holding Gmbh | Verfahren zur Herstellung eines Schiebemuffenrings |
| CN105598446A (zh) * | 2015-12-02 | 2016-05-25 | 董开 | 一种稀土永磁材料柔性成型的方法及装置 |
| DE102015224588A1 (de) * | 2015-12-08 | 2017-06-08 | Mahle International Gmbh | Verfahren zum Herstellen eines porösen Formkörpers |
| CN106521219B (zh) * | 2017-01-05 | 2018-07-03 | 重庆大学 | 一种TiC颗粒增强钛基多孔材料的制备方法 |
| CN106735185A (zh) * | 2017-03-15 | 2017-05-31 | 攀枝花学院 | 梯度多孔钛及其制备方法 |
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| AT210153B (de) | 1959-03-25 | 1960-07-25 | Plansee Metallwerk | Verfahren zur Bearbeitung von Formkörpern aus hochschmelzenden Metallen bzw. deren Legierungen |
| JPS49106958A (de) * | 1973-02-19 | 1974-10-11 | ||
| CN1019760B (zh) * | 1987-06-11 | 1992-12-30 | 国家机械工业委员会上海材料研究所 | 由球形金属粉末制造多孔元件的方法 |
| JPH02254103A (ja) * | 1989-03-28 | 1990-10-12 | Hitachi Powdered Metals Co Ltd | 焼結金属部品の製造方法 |
| US5510066A (en) * | 1992-08-14 | 1996-04-23 | Guild Associates, Inc. | Method for free-formation of a free-standing, three-dimensional body |
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| GB2289466B (en) * | 1994-05-10 | 1997-10-22 | Dytech Corp Ltd | Production of porous refractory articles |
| US5765095A (en) * | 1996-08-19 | 1998-06-09 | Smith International, Inc. | Polycrystalline diamond bit manufacturing |
| DE19636524A1 (de) * | 1996-09-09 | 1998-03-12 | Krebsoege Gmbh Sintermetall | Verfahren zur Herstellung eines gesinterten Bauteils |
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| DE19638927C2 (de) * | 1996-09-23 | 1998-07-16 | Forschungszentrum Juelich Gmbh | Verfahren zur Herstellung hochporöser, metallischer Formkörper |
| AT403692B (de) * | 1996-12-18 | 1998-04-27 | Electrovac | Verfahren zur herstellung von keramischen formkörpern |
| DE19726961C1 (de) * | 1997-06-25 | 1998-11-26 | Forschungszentrum Juelich Gmbh | Verfahren zur Herstellung poröser Formkörper aus Metall, Keramik oder Kompositwerkstoffen |
| JP2001059103A (ja) * | 1999-08-19 | 2001-03-06 | Injex Corp | 金属焼結体の製造方法 |
| US6491891B1 (en) * | 1999-09-10 | 2002-12-10 | Ut-Battelle, Inc. | Gelcasting polymeric precursors for producing net-shaped graphites |
| ES2212606T3 (es) * | 1999-09-14 | 2004-07-16 | Stratec Medical Ag | Mezcla de dos fases particulares para la produccion de un cuerpo verde apto para la sinterizacion a temperaturas elevadas. |
| US6254998B1 (en) * | 2000-02-02 | 2001-07-03 | Materials And Electrochemical Research (Mer) Corporation | Cellular structures and processes for making such structures |
| CN1174825C (zh) * | 2000-06-14 | 2004-11-10 | 太原艺星科技有限公司 | 一种异形精密多孔元件的制造方法 |
| JP3566637B2 (ja) * | 2000-08-25 | 2004-09-15 | 住友チタニウム株式会社 | 焼結チタンフィルタの製造方法 |
| US6524522B2 (en) * | 2001-03-07 | 2003-02-25 | Advanced Ceramics Research, Inc. | Method for preparation of metallic foam products and products made |
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-
2002
- 2002-06-03 DE DE10224671A patent/DE10224671C1/de not_active Expired - Fee Related
-
2003
- 2003-05-09 EP EP03737877A patent/EP1523390B1/de not_active Expired - Lifetime
- 2003-05-09 US US10/517,118 patent/US7147819B2/en not_active Expired - Lifetime
- 2003-05-09 JP JP2004508986A patent/JP4546238B2/ja not_active Expired - Fee Related
- 2003-05-09 ES ES03737877T patent/ES2307948T3/es not_active Expired - Lifetime
- 2003-05-09 CN CN038127814A patent/CN1863630B/zh not_active Expired - Fee Related
- 2003-05-09 WO PCT/DE2003/001484 patent/WO2003101647A2/de not_active Ceased
- 2003-05-09 AU AU2003245820A patent/AU2003245820B2/en not_active Ceased
- 2003-05-09 PL PL372178A patent/PL205839B1/pl unknown
- 2003-05-09 BR BRPI0311587-9A patent/BR0311587B1/pt not_active IP Right Cessation
- 2003-05-09 CA CA2488364A patent/CA2488364C/en not_active Expired - Fee Related
- 2003-05-09 AT AT03737877T patent/ATE399070T1/de active
- 2003-05-09 DE DE50310043T patent/DE50310043D1/de not_active Expired - Lifetime
-
2004
- 2004-12-23 ZA ZA2004/10364A patent/ZA200410364B/en unknown
- 2004-12-23 ZA ZA200410634A patent/ZA200410634B/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03101647A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1523390B1 (de) | 2008-06-25 |
| CA2488364C (en) | 2011-03-08 |
| CN1863630A (zh) | 2006-11-15 |
| CN1863630B (zh) | 2011-08-03 |
| JP4546238B2 (ja) | 2010-09-15 |
| WO2003101647A3 (de) | 2004-05-27 |
| BR0311587B1 (pt) | 2012-01-10 |
| JP2005531689A (ja) | 2005-10-20 |
| PL205839B1 (pl) | 2010-06-30 |
| ES2307948T3 (es) | 2008-12-01 |
| ZA200410634B (en) | 2006-06-28 |
| US20050249625A1 (en) | 2005-11-10 |
| ZA200410364B (en) | 2006-06-28 |
| BR0311587A (pt) | 2005-03-01 |
| DE50310043D1 (de) | 2008-08-07 |
| AU2003245820A1 (en) | 2003-12-19 |
| ATE399070T1 (de) | 2008-07-15 |
| WO2003101647A2 (de) | 2003-12-11 |
| PL372178A1 (en) | 2005-07-11 |
| US7147819B2 (en) | 2006-12-12 |
| DE10224671C1 (de) | 2003-10-16 |
| AU2003245820B2 (en) | 2009-01-08 |
| CA2488364A1 (en) | 2003-12-11 |
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| Publication | Publication Date | Title |
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