EP1565594A1 - Processus permettant d'ameliorer l'aptitude au faconnage a chaud d'un lingot de superalliage coule - Google Patents
Processus permettant d'ameliorer l'aptitude au faconnage a chaud d'un lingot de superalliage couleInfo
- Publication number
- EP1565594A1 EP1565594A1 EP03812051A EP03812051A EP1565594A1 EP 1565594 A1 EP1565594 A1 EP 1565594A1 EP 03812051 A EP03812051 A EP 03812051A EP 03812051 A EP03812051 A EP 03812051A EP 1565594 A1 EP1565594 A1 EP 1565594A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ingot
- canister
- metal
- set forth
- metal powder
- 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.)
- Withdrawn
Links
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 91
- 239000002184 metal Substances 0.000 claims abstract description 91
- 239000000843 powder Substances 0.000 claims abstract description 76
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 238000005253 cladding Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 3
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims 4
- 238000003466 welding Methods 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 9
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000005242 forging Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001247 waspaloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010275 isothermal forging Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009497 press forging Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910001088 rené 41 Inorganic materials 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
- C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/087—Coating with metal alloys or metal elements only
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
Definitions
- This invention relates to processes for hot working cast Ni, Fe and Co base alloy ingots, and in particular to a process for preparing a cast Ni base superalloy ingot so that it can be readily hot worked.
- the hot working of difficult to work alloys has been facilitated by providing the alloy in the form of prelate metal powder that has been hot isostatically pressed to substantially full density inside of a carbon or stainless steel canister.
- the canister serves as the pressure-transmitting medium through which the powder is consolidated during hot isostatic pressing.
- the canister also benefits the hot workability of the metal powder by limiting heat loss from the metal powder during subsequent hot working of the HIP'd powder. Further, the canister also provides a ductile surface zone that is less prone to checking and cracking.
- a process for preparing a superalloy ingot for hot working includes the steps of providing a cast ingot of a superalloy and inserting the ingot into a metal canister that is adapted to encapsulate it.
- the ingot is positioned within the steel canister so as to provide an annular space and end spaces between the ingot and the canister.
- Metal powder is filled into the annular space and end spaces between the ingot and the canister.
- the metal powder is selected to readily bond with the surfaces of the ingot and the canister.
- the canister is then closed (except for an evacuation tube) with the ingot and the metal powder inside. Gas and moisture are evacuated from the interior of the canister and the canister is then sealed.
- the canister with the ingot and the metal powder inside is hot isostatically pressed to produce an ingot assembly having a cladding formed about the entire ingot.
- a process for hot working a superalloy ingot includes the steps of providing a cast ingot ofa superalloy and inserting the ingot into a metal canister that is adapted to encapsulate it.
- Metal powder is initially poured into the bottom of the steel canister to form a layer that separates the ingot from the canister bottom.
- the ingot is then positioned within the steel canister so as to provide an annular space between the ingot and the canister.
- Metal powder is filled into the annular space.
- the metal powder is selected to readily bond with the surfaces of the ingot and the steel canister.
- the canister is closed except for an evacuation tube.
- Gas and moisture are evacuated from the interior of the canister through the evacuation tube, which is subsequently sealed.
- the canister with the ingot and the metal powder inside is hot isostatically pressed to form an assembly having a cladding formed about the entire ingot.
- the assembly is then heated to a temperature suitable for hot working the superalloy and then the assembly is hot worked to a desired shape and size.
- an assembly for facilitating the hot working of a superalloy ingot includes an ingot formed of a superalloy, a layer of cladding surrounding the ingot, and a layer of consolidated metal powder disposed between the ingot and the cladding and bonded to the ingot and the cladding layer.
- Figure 1 is a perspective view of a canister/ingot assembly used in the process according to this invention.
- Figure 2 is an elevation view of a cross section of the canister/ingot assembly shown in Figure 1 as viewed along line 2-2 therein;
- Figure 3 is a perspective view of an alternative embodiment of a canister/ingot assembly used in the process according to this invention.
- Figure 4 is an elevation view of a cross section of the canister/ingot assembly shown in Figure 3 as viewed along line 4-4 therein;
- the process according to the present invention preferably uses a generally cylindrical steel canister with a dome top to encapsulate an ingot of a superalloy.
- superalloy means an Fe-base, Co-base, and/or Ni-base alloy that contains chromium for resistance to oxidation and hot corrosion, and which may contain additional elements for providing high strength at elevated temperatures.
- the canister is preferably formed from low alloy or mild steel, although stainless steel could be used.
- An intermediate layer of metal powder is filled into the space between the steel canister and the cast superalloy ingot.
- the carbon steel canister provides a basic mold to contain the powder and the ingot.
- the canister is considered to be disposable because it is expected to scale heavily during the long time, high temperature heating cycles the ingot will undergo during the hot working operation.
- the canister can be readily formed from commonly available steel pipe and top dome that have an internal diameter that is larger than the largest diameter of the as- cast superalloy ingot.
- a tapered canister could be used, but such a canister must be specially rolled and welded to fit the tapered ingot.
- the canister is thin-walled, i.e., about 1/4-3/8 inch thick.
- the metal powder is preferably made from a stainless steel alloy such as Type 304 or Type 316 stainless steel.
- the metal powder can be a superalloy powder of the same or similar composition as the superalloy ingot, a non-ferrous alloy such as an 80Ni-20Cr alloy, or a mixture of either or both of those alloys with or without the stainless steel powder.
- Stainless steel powder has a lower thermal conductivity than carbon steel and provides thermal insulation at the surface of the cast ingot during hot working. Because of its composition the stainless steel powder layer does not scale as heavily as the steel canister. Consequently, a significant amount of the stainless steel will remain on the surface of the cast ingot during the thermal and deformation cycles undergone by the ingot. Readily available stainless steel powder can be used to fill the annular spacing between the ingot and the steel canister.
- Austenitic stainless steel powders such as Type 304 and Type 316L powders, are ductile and do not undergo a hardening phase transformation that could cause cracking during the hot working process. Prior to being used in this process, the metal powder is preferably baked at about 250°F to remove any moisture therefrom.
- the canister is sized to accommodate a powder layer that is about Vi inch to about 7/8 inch thick along the length of the ingot and at least about 3/4 inch to 1 inch thick at the ends of the ingot. Although thicker powder layers could by used, a thinner powder layer permits the as-consolidated powder to flow more like the core ingot material, particularly at the ends of the canister/ingot assembly. This permits the ingot manipulator to grab more of the ingot material during hot working operations, thereby avoiding delamination of the cladding from the ingot.
- the superalloy ingot that is to be used is prepared to remove virtually all traces of surface porosity, oil, grease, and oxidation from all of its surfaces. This is done typically by Tysaman grinding of the ingot's longitudinal surface, hand grinding of the ingot ends, and hand wiping of all of the ingot surfaces with solvent, such as reagent grade acetone. These surface cleaning operations are performed to foster bonding between the ingot and the metal powder during HIP'ng.
- the ends of the ingot are also tapered to remove sharp edges that could cut through the consolidated metal powder during forging.
- the ingot is also preferably baked out at about 250 °F to remove any residual solvent and moisture on the ingot surface prior to insertion into the steel canister.
- the preferred procedure for forming the ingot/canister assembly is to place a layer of the powder into the canister at one end thereof.
- the ingot is then placed partially within the bottom part of the steel canister so as to provide an annular space between all other surfaces of the ingot and the steel canister.
- Metal powder is filled into the annular space up to within about 4 inches of the top of the bottom section of the canister.
- the metal powder is selected to readily bond with the surfaces of the ingot and the steel canister.
- the top part of the canister is then positioned over the top end of the ingot and an argon purge gas is applied through a tube inserted through the top of the top part of the canister to remove air from the interior of the canister.
- the top part of the canister is welded onto the bottom part of the canister, which seals the canister, except for a powder fill hole located in the top part of the canister. Additional powder is then filled into the top section of the canister, filling the annular spacing between the top and side of the ingot and the interior of the canister. Vibration filling of the powder is preferred to obtain the best fill density.
- a metal closure plate, containing an evacuation tube is then placed onto and welded to the top part of the canister, sealing the canister except for the evacuation tube.
- a stainless steel mesh screen typically -325 mesh, is welded to the bottom end of the evacuation tube in the disk opening to prevent powder from being pulled out of the canister during a subsequent evacuation step.
- the canister/ingot assembly 50 includes an ingot 10 of a superalloy such as PYROMET 720 or Super WASPALOY.
- the ingot 10 is disposed in a steel canister 20 and a layer 30 of stainless steel powder is provided between the ingot 10 and the canister 20 along the length and ends thereof.
- An evacuation tube 40 is welded into a central opening in the top end 22 of the canister 20.
- the canister/ingot assembly 350 includes an ingot 310 of a superalloy.
- the ingot 310 is disposed in a steel canister 320 having a domed top portion 322 and a generally cylindrical bottom portion 324. In this arrangement, the ingot 310 is longer than the bottom portion 324.
- the ingot 310 is chamfered or tapered at the end proximate the domed top portion 322 to remove a sharp edge that could cut through the consolidated metal powder and the canister during hot working.
- a layer 330 of stainless steel powder is provided between the ingot 310 and the canister 320 along the length and ends thereof.
- An evacuation tube 340 is welded into a central opening in the domed top portion 322 of the canister 320. As described above, a fine mesh screen 360 is welded to the bottom end of tube 340.
- the canister/ingot assembly When the canister/ingot assembly is fully assembled, it is placed into a furnace or oven. The evacuation tube is connected to a vacuum pump. The canister/ingot assembly is then hot outgassed to remove substantially all moisture and oxygen from the metal powder. To that end, the canister/ingot assembly is heated at an elevated temperature, preferably about 250-400 °F while a vacuum of less than about 200 microns of Hg is applied to the interior of the assembly. The canister/ingot assembly is maintained at the temperature and vacuum conditions until the pressure inside the canister reaches a minimum, at which time the out gassing step is terminated.
- the evacuation tube is then hot crimped, sealed and cut and the assembly is hot isostatically pressed (HIP'd) to substantially full densify the metal powder.
- HEP'd hot isostatically pressed
- HTP'ng not only consolidates the metal powder, but also causes it to bond to both the steel canister and to the superalloy ingot. Additionally, during the HIP'ng step, the powder is forced into any porosity on the surface of the ingot, thereby eliminating such porosity as a delamination or crack initiation source during subsequent hot working.
- the canister/ingot assembly is an integral body comprising the superalloy and a cladding composed of the steel canister and the consolidated metal powder interlayer.
- the clad ingot is then heated and hot worked in the usual manner to make a desired product form such as bar or billet.
- the ingot/cladding assembly is readily hot worked, such as by upsetting and press forging, according to known thermo-mechanical processing techniques. When the desired billet size and shape are obtained, any cladding remaining on the superalloy material is removed, preferably by a machining or grinding operation.
- an ingot of PYROMET 720 steel alloy was prepared and clad as described above in accordance with the process of this invention.
- the clad ingot was then upset and drawn on a forging press. No canister delamination was noted during these operations.
- the clad ingot was subjected to a second heating and forging cycle. Inspection of the forged billet after the second cycle showed essentially no surface or end cracking or canister delamination occurred (i.e. only minor local cracking or canister delamination was observed).
- the cladding was ground off the longitudinal surface of the forged billet and the billet was then processed to a nominal 6" rd. bar.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Powder Metallurgy (AREA)
Abstract
La présente invention concerne un processus de préparation de lingot de superalliage à base de Ni, Fe et Co en vue d'un façonnage à chaud et d'un ensemble lingot fabriqué par ce processus. Ce processus consiste à prendre un lingot coulé et à introduire ce lingot dans un récipient d'acier dimensionné de façon à contenir complètement ce lingot. Le lingot est placé à l'intérieur de ce récipient d'acier de manière à laisser un espace entre ce lingot et le récipient d'acier. Après le placement du lingot dans le récipient d'acier, de la poudre de métal est versée dans cet espace. Cette poudre de métal est sélectionnée de façon à se lier immédiatement avec les surfaces du lingot et du récipient d'acier. Puis, le récipient d'acier est refermé avec le lingot et la poudre de métal présents à l'intérieur. Le gaz et l'humidité sont retirés de l'intérieur de ce récipient d'acier. Ce récipient d'acier avec le lingot et la poudre de métal présents à l'intérieur est pressé à chaud ne manière isostatique afin de former un ensemble lingot possédant une chemise tout autour des surfaces longitudinales et des surfaces d'extrémité de ce lingot. L'ensemble lingot produit à partir de ce processus est immédiatement façonné à chaud sans dommages importants causé au lingot par des craquelures ou des craquelures en quadrillages.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42920902P | 2002-11-26 | 2002-11-26 | |
| US429209P | 2002-11-26 | ||
| PCT/US2003/037933 WO2004048641A1 (fr) | 2002-11-26 | 2003-11-26 | Processus permettant d'ameliorer l'aptitude au façonnage a chaud d'un lingot de superalliage coule |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1565594A1 true EP1565594A1 (fr) | 2005-08-24 |
Family
ID=32393524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03812051A Withdrawn EP1565594A1 (fr) | 2002-11-26 | 2003-11-26 | Processus permettant d'ameliorer l'aptitude au faconnage a chaud d'un lingot de superalliage coule |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20040105774A1 (fr) |
| EP (1) | EP1565594A1 (fr) |
| AU (1) | AU2003297577A1 (fr) |
| WO (1) | WO2004048641A1 (fr) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8230899B2 (en) * | 2010-02-05 | 2012-07-31 | Ati Properties, Inc. | Systems and methods for forming and processing alloy ingots |
| US9267184B2 (en) * | 2010-02-05 | 2016-02-23 | Ati Properties, Inc. | Systems and methods for processing alloy ingots |
| US10207312B2 (en) | 2010-06-14 | 2019-02-19 | Ati Properties Llc | Lubrication processes for enhanced forgeability |
| US8789254B2 (en) | 2011-01-17 | 2014-07-29 | Ati Properties, Inc. | Modifying hot workability of metal alloys via surface coating |
| US9120150B2 (en) | 2011-12-02 | 2015-09-01 | Ati Properties, Inc. | Endplate for hot isostatic pressing canister, hot isostatic pressing canister, and hot isostatic pressing method |
| US9027374B2 (en) | 2013-03-15 | 2015-05-12 | Ati Properties, Inc. | Methods to improve hot workability of metal alloys |
| US9539636B2 (en) | 2013-03-15 | 2017-01-10 | Ati Properties Llc | Articles, systems, and methods for forging alloys |
| JP6645215B2 (ja) | 2016-01-28 | 2020-02-14 | 大同特殊鋼株式会社 | 合金塊の製造方法 |
| CN111014622B (zh) * | 2019-12-25 | 2021-12-31 | 广西大学 | 一种低熔点金属和异种高熔点金属扩散偶的制备方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3398448A (en) * | 1966-09-12 | 1968-08-27 | Int Nickel Co | Process for coating steel with nickel |
| DE3109602C2 (de) * | 1981-01-31 | 1983-01-13 | Klöckner-Werke AG, 4100 Duisburg | Verfahren und Vorrichtung zum Herstellen plattierter Blöcke |
| US4567936A (en) * | 1984-08-20 | 1986-02-04 | Kaiser Aluminum & Chemical Corporation | Composite ingot casting |
| EP0283877B1 (fr) * | 1987-03-25 | 1993-06-23 | Nippon Steel Corporation | Procédé pour la fabrication de tubes de métal enrobé. |
| GB2239200A (en) * | 1989-04-07 | 1991-06-26 | Ici Plc | Making explosively clad metal sheet |
| US5462575A (en) * | 1993-12-23 | 1995-10-31 | Crs Holding, Inc. | Co-Cr-Mo powder metallurgy articles and process for their manufacture |
| US6511630B1 (en) * | 1999-10-04 | 2003-01-28 | General Electric Company | Method for forming a coating by use of foam technique |
| IL158081A0 (en) * | 2001-03-27 | 2004-03-28 | Crs Holdings Inc | Stainless steel alloy and elongated strips formed thereof |
-
2003
- 2003-11-26 WO PCT/US2003/037933 patent/WO2004048641A1/fr not_active Ceased
- 2003-11-26 EP EP03812051A patent/EP1565594A1/fr not_active Withdrawn
- 2003-11-26 US US10/722,979 patent/US20040105774A1/en not_active Abandoned
- 2003-11-26 AU AU2003297577A patent/AU2003297577A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2004048641A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040105774A1 (en) | 2004-06-03 |
| AU2003297577A1 (en) | 2004-06-18 |
| WO2004048641A1 (fr) | 2004-06-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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