EP1425121A1 - Procede de realisation de pieces moulees, sable de coulee, et son utilisation pour la mise en oeuvre du procede - Google Patents
Procede de realisation de pieces moulees, sable de coulee, et son utilisation pour la mise en oeuvre du procedeInfo
- Publication number
- EP1425121A1 EP1425121A1 EP02772298A EP02772298A EP1425121A1 EP 1425121 A1 EP1425121 A1 EP 1425121A1 EP 02772298 A EP02772298 A EP 02772298A EP 02772298 A EP02772298 A EP 02772298A EP 1425121 A1 EP1425121 A1 EP 1425121A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- casting
- molding material
- mold
- binder
- molding
- 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
- 238000005266 casting Methods 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003110 molding sand Substances 0.000 title description 3
- 239000012778 molding material Substances 0.000 claims abstract description 68
- 239000011230 binding agent Substances 0.000 claims abstract description 53
- 239000012634 fragment Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000007711 solidification Methods 0.000 claims abstract description 7
- 230000008023 solidification Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 238000000465 moulding Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052863 mullite Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims 2
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000004576 sand Substances 0.000 abstract description 9
- 230000009969 flowable effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000006004 Quartz sand Substances 0.000 description 12
- 239000000155 melt Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/08—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for decreasing shrinkage of the mould, e.g. for investment casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/10—Cores; Manufacture or installation of cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
Definitions
- the invention relates to a molding material and its use for the production of casting mold parts which are used for the casting of molten metal, in particular of molten light metal, such as molten aluminum.
- casting mold parts can be, for example, casting cores, through which cavities are formed in the interior of the casting to be produced.
- mold parts according to the invention can be components from which a multi-part mold is assembled, by means of which the outer shape of the cast part to be produced is determined.
- such casting mold parts are required, by means of which the inner and the outer shape of the workpiece to be cast are determined. Accordingly, such casting mold parts can be casting cores, through which cavities are formed in the interior of the casting to be produced, or are casting mold elements from which a multi-part casting mold is assembled, which determines the external shape of the casting to be produced.
- quartz sand as the basic material for the production of casting mold parts has proven itself in several ways, in particular in the field of casting light metal materials. Such quartz sand can be obtained inexpensively and is characterized by simple processability and good quality in the imaging of the mold elements of the casting mold part to be produced.
- the molded materials should be regenerable after use in such a way that the highest possible rate of reuse is achieved with the molded raw material.
- This can be achieved in a manner known per se by using inorganic binders which release low emissions during the production of the molded parts and which can be burned almost without residue after the casting process has ended by exposure to sufficiently high temperatures.
- Another problem with pouring complex shaped castings using conventionally produced mold parts is that the sand is difficult to remove from the casting after cooling.
- the cast part is usually shaken or subjected to impacts which are intended to disintegrate the casting cores located in the inside of the cast part and the shaped parts adhering to the outside of the cast part and to promote the trickling out of the molded material particles obtained.
- these mechanical methods for removing the molded parts entail the risk of damage to the cast part. This can lead to the formation of cracks, particularly in the case of filigree-shaped or thin-walled components.
- the object of the invention was to provide a method with which high-quality, complex-shaped castings can be produced and in which the casting mold parts can be removed from or from the casting in a simple and safe manner after the casting process has ended.
- a molding material should be made available, with which molded parts can be produced which are suitable for producing high-quality, complex-shaped castings and which can be easily and safely removed from or from the casting after the casting process has ended.
- the above-mentioned object is achieved by a molding material for the production of casting mold parts for pouring molten metal, in particular light metal melt, which consists of a mixture of a free-flowing mold base material inert to the metal melt and a binder mixed with the mold base material, the thermal expansion behavior of mold base material and binder are matched to one another in such a way that the thermal expansion coefficient of the molten metal is above the thermal expansion coefficient of the casting mold part produced from the molding material.
- the invention is based on the knowledge that, by choosing a suitable molding material, mold parts can be produced which optimally combine the properties required for the simple, safe and environmentally friendly production of high-quality, dimensionally accurate cast parts.
- the molding material according to the invention optimally combines the properties which are a prerequisite for the production of a high-quality cast part are at the same time a simple manufacturing method.
- the molding material according to the invention contains a granular or comparable particle-like form and as such a free-flowing base material which, when it inevitably occurs during the casting, exhibits a significantly low thermal expansion compared to conventionally used quartz sand.
- the basic molding material thus guarantees high dimensional accuracy in the production of complex shaped castings, even with a low material thickness.
- the free-flowing base material is mixed with a binder that has a different expansion behavior from the base material when heated. Due to the different thermal expansion of the base material and the binder, the binder is detached from the grains of the base material after the heat has been introduced from the casting heat. As a result, when the binder expands more than the base material, the binder bursts open so that it loses its solid shape and can be easily removed from or from the cast part. Conversely, the expansion behavior of the basic molding material can be such that the bond to the binder is broken by a change in volume associated with the heating and the basic material becomes free-flowing again. It is essential that the core or molded component breaks along with the heating, so that after the casting has cooled, it breaks down into easily removable, loose individual parts.
- a further property of the molding material procured and used according to the invention which is advantageous for the invention is that the binder and the molding base material are matched to one another such that the particles of the base material are thermally stable and not elastically bound by the binder in the molded parts produced from the molding material.
- the cast part produced from such a basic molding material behaves brittle over the entire temperature interval that has passed through when the melt is poured off, as a result of which the Invention desired breaking of the molded parts is promoted.
- a further advantageous embodiment of the invention is that the particles of the basic molding material have an essentially round, spherical shape.
- the spherical shape of the base material and the associated predominance of point contacts between the base material particles promotes the automatic disintegration of the molded parts as a result of the mechanical forces that occur during the pouring and solidification of the melt.
- a basic molding material that fulfills this requirement particularly well is synthetically produced mullite.
- the molding base material has at least a portion, preferably more than 50% or more than 70%, of the aluminum oxide sand (mullite) which constitutes quartz sand.
- Mullite has a round grain shape and a density comparable to that of quartz sand.
- molded material composed according to the invention is particularly suitable for the production of casting cores. These can be removed after casting without the risk of damaging the finished casting.
- a molding base material composed of a mullite-quartz sand mixture and a molding material produced from it have a rather insulating effect. Therefore, these substances can be used specifically for casting technology applications in which there is a temperature rise above the critical temperature of 573 ° C for quartz sands, in which the thermal conductivity of the molded parts produced from the substances in question plays a subordinate role or heat conduction should be deliberately restricted. Practical tests have shown that by adding a sufficient amount of mullite sand to a quartz sand, the problems of spontaneous changes in geometry can be overcome, which occur when quartz sand is used alone as the basic molding material for the production of slim, filigree castings. It is essential that the proportion of Al 2 Si0 5 sand is sufficiently high in each case to be able to compensate for the change in length of the quartz that otherwise occurs with quartz sand due to the heating above the critical temperature.
- the binder and base material are moreover preferably matched to one another in such a way that a casting mold part produced from the molding material has a low thermal conductivity. This property causes the temperature difference between the casting material and the molded part to remain large after the metal melt has been poured off, so that the risk of premature thermally or chemically triggered decomposition of the molded part is reduced to a minimum.
- the base material and the binder expand differently.
- the binder after the heat input from the casting heat, the binder is detached from the grains of the base material.
- the binder expands more than the base material, it bursts the molded part in such a way that it loses its solid form and breaks up into fragments. These can easily be shaken off or from the cast part without the risk of mechanical damage.
- the mold part becomes so solid that it can be removed from the core box and placed in a heating device, for example a microwave oven, which is arranged outside the core box.
- a heating device for example a microwave oven, which is arranged outside the core box.
- this heating device it is heated with sufficient heat output to such an extent that an amount of water sufficient for complete hardening is withdrawn.
- the respective molded part can be used to increase the molded part
- Core surface strength can be sprayed with binder liquid.
- the molded parts treated in this way have an increased stability with an equally increased abrasion resistance, so that they can be stored without problems and meet the highest requirements for their dimensional accuracy. This proves to be particularly favorable with regard to an optimized quality of the casting to be produced if a water glass binder is used.
- the invention is explained in more detail below on the basis of a drawing illustrating an exemplary embodiment.
- the single figure shows schematically in section a camshaft core 1 of a mold, not shown, for casting a cylinder head from an aluminum casting alloy.
- two recesses 3, 4 are formed, spaced apart in the longitudinal direction, through which the shape of the bearing blocks of the cylinder head to be manufactured, which are provided for mounting the camshaft, is determined.
- the length A of the branches 5, 6 is in this case many times greater than its diameter B.
- the length C of the main section 7 of the oil channel core 8 is many times greater than its diameter D.
- the ole channel core 8 has been produced in a conventional manner in a conventional molding machine from a molding material according to the invention which has been produced by mixing a molding base material consisting of mullite sand and quartz sand with a water glass binder. Due to the proportion of mullite sand, it is ensured that the ole channel core 8 expands evenly and consequently clearly predeterminable even when it heats up to over 573 ° C. in the course of the casting of the cylinder head to be produced.
- the casting cores 1.8 deform due to the peculiarities coordinated with one another in the manner according to the invention only insignificant of the basic molding material and binder.
- the low thermal expansion of the base material thus supports the process-reliable achievement of the dimensional requirements of the casting.
- the fragments into which the respective casting core 1, 8 automatically disintegrates due to the action of the casting heat and due to the different thermal expansion behavior of the base material and the binder , emptied from the casting and processed.
- the solid core contraction of the cast metal which is considerably higher than that of the casting cores 1.8, subjects the casting core 1.8 to high mechanical stresses. Due to the brittle, inelastic nature of the casting cores 1.8, these cause the casting cores 1.8 to shatter into bulb-like fragments.
- the processing of the casting core fragments can include gentle breaking into granular particles.
- the granular particles obtained can then be subjected to metal deposition and dedusting to produce the condition necessary for their reuse.
- the casting mold parts recycled to granular material are then used again as the base material for the molding material composed according to the invention.
- molding materials are used in the manner according to the invention which consist of molding base material, such as synthetic mullite, mixed with water glass binder, then no significant emissions occur during the production of the moldings. As a result, casting errors that occur repeatedly as a result of gas formation, extensive precautions for the extraction of gases and complex tool cleaning can be avoided in the conventional procedure. This reduces the burden on the environment and operating personnel to a minimum.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10145417A DE10145417A1 (de) | 2001-09-14 | 2001-09-14 | Formgrundstoff, Formstoff und Formteil für eine Giessform |
DE10145417 | 2001-09-14 | ||
DE10209183A DE10209183A1 (de) | 2002-03-04 | 2002-03-04 | Formstoff für die Herstellung von Gießformteilen |
DE10209224A DE10209224A1 (de) | 2002-03-04 | 2002-03-04 | Verfahren zum Herstellen von Gußstücken |
DE10209183 | 2002-03-04 | ||
DE10209224 | 2002-03-04 | ||
PCT/EP2002/010301 WO2003024642A1 (fr) | 2001-09-14 | 2002-09-13 | Procede de realisation de pieces moulees, sable de coulee, et son utilisation pour la mise en oeuvre du procede |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1425121A1 true EP1425121A1 (fr) | 2004-06-09 |
EP1425121B1 EP1425121B1 (fr) | 2006-04-19 |
Family
ID=27214603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02772298A Expired - Lifetime EP1425121B1 (fr) | 2001-09-14 | 2002-09-13 | Procede de realisation de pieces moulees, sable de coulee, et son utilisation pour la mise en oeuvre du procede |
Country Status (14)
Country | Link |
---|---|
US (1) | US20040261969A1 (fr) |
EP (1) | EP1425121B1 (fr) |
JP (1) | JP2005502473A (fr) |
KR (1) | KR20040070330A (fr) |
CN (1) | CN1298456C (fr) |
AT (1) | ATE323563T1 (fr) |
BR (1) | BR0212534A (fr) |
CA (1) | CA2461797A1 (fr) |
DE (1) | DE50206490D1 (fr) |
ES (1) | ES2262845T3 (fr) |
HU (1) | HUP0401547A2 (fr) |
MX (1) | MXPA04002424A (fr) |
PL (1) | PL367736A1 (fr) |
WO (1) | WO2003024642A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10321106A1 (de) * | 2003-05-09 | 2004-12-23 | Hydro Aluminium Deutschland Gmbh | Formstoff, Formteil und Verfahren zur Herstellung von Formteilen für eine Gießform |
EP1956786A3 (fr) | 2005-09-30 | 2010-05-12 | Nortel Networks Limited | Canal d'accès initial pour réseau de communication mobile extensible sans fil |
CN1319669C (zh) * | 2005-12-20 | 2007-06-06 | 金啸海 | 一种用于铸造的型砂及其制备方法 |
EP2216112A1 (fr) * | 2009-02-10 | 2010-08-11 | Siemens Aktiengesellschaft | Pièce coulée à base de nickel doté d'un corps de compensation et procédé de fabrication d'une pièce coulée à base de nickel |
RU2635598C2 (ru) * | 2013-09-04 | 2017-11-14 | Немак, С.А.Б. Де К.В. | Способ извлечения из формы для литья литой заготовки, отлитой из лёгкого сплава |
DE102014110826A1 (de) | 2014-07-30 | 2016-02-04 | Fritz Winter Eisengiesserei Gmbh & Co. Kg | Verfahren zum Gießen von Gussteilen |
KR101663084B1 (ko) * | 2016-03-18 | 2016-10-06 | 박성제 | 정밀 주조를 통해 거푸집을 용이하게 제거할 수 있는 수도꼭지 제조 방법 |
CN111822677A (zh) * | 2019-04-11 | 2020-10-27 | 上海航天精密机械研究所 | 一种基于复合铸型的轻金属铸造方法 |
DE102020208692A1 (de) | 2020-07-10 | 2022-01-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Verfahren zur Herstellung und Entfernung eines Gießkerns sowie zur Verwendung des Gießkerns |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS544817A (en) * | 1977-06-15 | 1979-01-13 | Hitachi Ltd | Selffhardening casting sand |
JPS5584251A (en) * | 1978-12-22 | 1980-06-25 | Hitachi Ltd | Casting method |
EP0214987A1 (fr) * | 1984-06-12 | 1987-03-25 | Mikrovagsapplikation Ab | Boite a noyaux et son procede de fabrication |
GB9308363D0 (en) * | 1993-04-22 | 1993-06-09 | Foseco Int | Refractory compositions for use in the casting of metals |
JPH07164102A (ja) * | 1993-12-13 | 1995-06-27 | Mazda Motor Corp | 鋳造用砂鋳型およびその製造方法 |
JP3186005B2 (ja) * | 1993-12-24 | 2001-07-11 | 愛知機械工業株式会社 | 鋳造用中子 |
US5612393A (en) * | 1993-12-24 | 1997-03-18 | Nissan Motor Co., Ltd. | Casting core composition |
CN1041064C (zh) * | 1994-07-05 | 1998-12-09 | 江苏理工大学 | 一种再生砂制备有机酯水玻璃自硬砂的方法 |
CN1071159C (zh) * | 1995-11-08 | 2001-09-19 | 花王株式会社 | 砂型用粘结剂、型砂组合物和砂型的制造方法 |
US6371194B1 (en) * | 1996-08-09 | 2002-04-16 | Vaw Aluminium Ag | Method for producing core preforms and recycling core sand for a foundry |
DE19632293C2 (de) * | 1996-08-09 | 1999-06-10 | Thomas Prof Dr In Steinhaeuser | Verfahren zur Herstellung von Kernformlingen für die Gießereitechnik |
-
2002
- 2002-09-13 US US10/489,485 patent/US20040261969A1/en not_active Abandoned
- 2002-09-13 ES ES02772298T patent/ES2262845T3/es not_active Expired - Lifetime
- 2002-09-13 CA CA002461797A patent/CA2461797A1/fr not_active Abandoned
- 2002-09-13 MX MXPA04002424A patent/MXPA04002424A/es active IP Right Grant
- 2002-09-13 AT AT02772298T patent/ATE323563T1/de not_active IP Right Cessation
- 2002-09-13 CN CNB02820431XA patent/CN1298456C/zh not_active Expired - Fee Related
- 2002-09-13 PL PL02367736A patent/PL367736A1/xx unknown
- 2002-09-13 WO PCT/EP2002/010301 patent/WO2003024642A1/fr active IP Right Grant
- 2002-09-13 HU HU0401547A patent/HUP0401547A2/hu unknown
- 2002-09-13 EP EP02772298A patent/EP1425121B1/fr not_active Expired - Lifetime
- 2002-09-13 BR BR0212534-0A patent/BR0212534A/pt not_active IP Right Cessation
- 2002-09-13 JP JP2003528331A patent/JP2005502473A/ja active Pending
- 2002-09-13 KR KR10-2004-7003845A patent/KR20040070330A/ko not_active Application Discontinuation
- 2002-09-13 DE DE50206490T patent/DE50206490D1/de not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO03024642A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2005502473A (ja) | 2005-01-27 |
HUP0401547A2 (hu) | 2005-08-29 |
WO2003024642A1 (fr) | 2003-03-27 |
ATE323563T1 (de) | 2006-05-15 |
US20040261969A1 (en) | 2004-12-30 |
PL367736A1 (en) | 2005-03-07 |
EP1425121B1 (fr) | 2006-04-19 |
ES2262845T3 (es) | 2006-12-01 |
MXPA04002424A (es) | 2005-04-11 |
BR0212534A (pt) | 2004-10-19 |
CA2461797A1 (fr) | 2003-03-27 |
CN1298456C (zh) | 2007-02-07 |
CN1599651A (zh) | 2005-03-23 |
DE50206490D1 (de) | 2006-05-24 |
KR20040070330A (ko) | 2004-08-07 |
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