EP0909346A1 - Procede et installation de revetement electrolytique par une couche metallique de la surface d'un cylindre pour coulee continue de bandes metalliques minces - Google Patents
Procede et installation de revetement electrolytique par une couche metallique de la surface d'un cylindre pour coulee continue de bandes metalliques mincesInfo
- Publication number
- EP0909346A1 EP0909346A1 EP97927245A EP97927245A EP0909346A1 EP 0909346 A1 EP0909346 A1 EP 0909346A1 EP 97927245 A EP97927245 A EP 97927245A EP 97927245 A EP97927245 A EP 97927245A EP 0909346 A1 EP0909346 A1 EP 0909346A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- casting surface
- masks
- edges
- casting
- electrolyte
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims abstract description 16
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 238000009749 continuous casting Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000009434 installation Methods 0.000 title claims description 19
- 238000005266 casting Methods 0.000 claims abstract description 40
- 230000033001 locomotion Effects 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000011810 insulating material Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims 1
- 238000000429 assembly Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 57
- 229910052759 nickel Inorganic materials 0.000 description 29
- 239000010410 layer Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Definitions
- the invention relates to the continuous casting of metals. More specifically, it relates to the conditioning of the external surface of the cylinder or cylinders which constitute the movable wall or walls of the molds for continuous casting of thin strips of metals such as steel.
- the ingot molds for continuous casting machines of steel strips a few mm thick between two cylinders directly from liquid metal have a casting space defined by the lateral surfaces of two cylinders rotating in opposite directions around their axes kept horizontal and by two refractory side plates pressed against the edges of the cylinders.
- These cylinders have a diameter of up to 1500 mm and a width which, on current experimental installations, is approximately 600 to 800 mm. But, in the long term, this width will have to reach 1300 to 1500 mm to meet the productivity requirements of an industrial installation.
- These cylinders are most often formed by a steel core around which is fixed a ferrule made of copper or copper alloy, cooled by a circulation of water between the core and the ferrule or internal to the ferrule.
- the surface of the shell which is intended to come into contact with the liquid metal can be coated with a metallic layer, most often nickel, of which l thickness generally reaches 1 to 2 mm.
- This layer of nickel makes it possible to adjust the heat transfer coefficient of the shell to an optimal value (lower than if the metal was brought directly into contact with copper) so that the solidification of the metal takes place under good metallurgical conditions: too rapid solidification would cause defects on the surface of the product.
- This adjustment is made by varying the thickness and the structure of the nickel layer.
- the nickel deposition is preferably carried out by an electrolytic route, as follows.
- the new ferrule (or previously partially or totally nickel-free), which is generally in the form of a hollow cylinder made of copper or copper alloy such as a copper - chromium (1%) - zirconium (0, 1%) alloy , went up on a tree, thanks to which it can easily be transported from one treatment station to another in the nickel-plating / nickel-plating workshop.
- the ferrule After having undergone various preparatory surface treatments (polishing, degreasing, acid pickling, etc.) aimed at improving the adhesion of nickel to copper, the ferrule is brought to the electrolytic nickel-plating station.
- This station consists of a tank containing the nickel-plating solution, above which the tree can be placed in a horizontal position and rotated around its axis. The lower part of the ferrule is thus soaked in the tank, and the rotation of the shaft-ferrule assembly at a speed of approximately 10 rpm, for example, makes it possible to carry out the treatment of the entire the ferrule.
- the ferrule constitutes the cathode
- the anode can be constituted by one or more anode titanium baskets immersed in the tank, closed by thin membranes, facing the surface of the ferrule and containing nickel beads. If you also want to coat with nickel a large fraction of the edges of the shell (which, during casting, will rub against the side plates in refractory and are therefore likely to wear), there are other anodic baskets facing these chants. Other types of anodes (soluble or insoluble) can also be used.
- the shell As a variant, it is possible to provide for the shell to remain fixed and for the electrolyte to pass past it. The main thing is therefore to create a relative movement between the shell and the electrolyte which ensures the continuous renewal of their interface.
- the nickel deposit is subjected to intense stresses, both mechanical and thermal. And we often see after just a few flows the appearance, near the edges of the cylinders, of cracks in the nickel deposit. These cracks relate to areas a few cm wide from the edges of the shell. They can lead to the formation of defects on the surface of the cast product, since they make its cooling heterogeneous. Above all, they constitute weak points from which very rapid degradation of the entire nickel deposit can begin.
- the object of the invention is to improve the performance of resistance to thermo-mechanical stresses of the metallic coating of the shell, by delaying as much as possible, or even by suppressing the appearance of cracks on the edges, so as to extend the average duration of use of the ferrule between two repairs to its coating.
- the subject of the invention is a method of electrolytic coating with a metal layer of the casting surface of a cylinder for the continuous casting of thin metal strips between two cylinders or on a single cylinder, according to which said surface is at least partially immersed.
- the invention also relates to an installation for electrolytic coating with a metal layer on the casting surface of a cylinder for the continuous casting of thin metal strips between two cylinders or on a single cylinder, of the type comprising a tank containing an electrolyte containing a salt of the metal to be deposited, means for at least partially immersing said casting surface in said tank and for creating a relative movement between said casting surface and said electrolyte, at least one anode disposed in the tank facing said surface casting, and means for bringing said casting surface to a cathodic potential, characterized in that it comprises masks of an insulating material interposed between the edges of said casting surface and said one or said anodes, said masks avoiding a concentration of streamlines on said edges.
- said masks have a general shape in an arc of a circle whose center of curvature is the same as that of the edge of the casting surface to which they face, and have two parallel edges each placed in the extension of said edge at the same distance "d" from it and connected by a wedge-shaped notch whose sides are perpendicular to each other.
- the invention consists in carrying out the electrolytic deposition of the metal coating by placing insulating masks in the vicinity of the edges of the ferrules. These masks, a preferred example of which is described, aim to obtain a regular distribution of the current lines in the edge areas of the ferrule. This gives the deposit a uniform thickness in these areas, in accordance with the desired nominal thickness.
- the inventors have found that there is a correlation between the speed of the appearance of cracks in the nickel coating at the edges of the shell and the regularity of the thickness of this deposit in these same areas, in particular on the right edges.
- the nominal thickness of the deposit is 2 mm over most of the surface of the shell, it can be seen that this thickness sometimes exceeds 7 mm in line with the edges.
- the inventors have found that the most reliable way to obtain a very homogeneous nickel deposit on the edges of the shell and in their immediate vicinity is to have insulating masks, preferably of a determined configuration, at a short distance from the edges, and that under these conditions, it was possible to suppress the early appearances of cracks in the coating of the edges of the ferrules.
- FIG. 1 which shows schematically a cross-sectional profile view along I-I an installation for coating a cylinder shell for casting between cylinders suitable for implementing the method according to the invention
- Figure 1 shows in cross section an installation according to the invention, the cutting plane being located inside the tank 1 containing the electrolyte solution 2 whose main component is a nickel salt, but in front of the shell made of copper 3 placed as a cathode and two anodes 4, 4 ′ arranged in the bottom of the tank 1.
- the ferrule 3, of cylindrical external shape and with an external diameter of 1500 mm, is mounted on a shaft 5 whose axis 6, during the electroplating operation, is rotated by means not shown. At least the lower part of the shell 3 is immersed in the electrolyte solution 2.
- the anodes 4, 4 ′ are soluble anodes formed by anodic baskets of titanium of curved shape, filled with nickel granules .
- the anodes 4, 4 ′ extend behind the cutting plane over a width greater than that of the ferrule 3. Facing the banks of the ferrule 3 are arranged masks 7, 7 ′ (7 being the only one visible in FIG. 1 ) an insulating material such as a polymer, the function of which is to prevent the current lines coming from the anodes 4, 4 ′ from reaching directly the edges and the edges of the ferrule 3, in order to avoid excess thicknesses of the deposit of nickel at their level.
- the positions of these masks 7, T with respect to the shell 3 can be adjusted by positioning means symbolized by movable rods 8.
- these masks 7, 7 ′ are in the form of tubes of substantially square or rectangular section, having the general shape of an arc of a circle, the center of curvature is the same as that of the edge of the ferrule 3 which they face.
- Their upper edge closest to the shore where their action is exerted has a notch 9, 9 'in the form of a corner, the two edges 10, 10' of which are perpendicular and of substantially equal lengths, for example of the order of 5 mm.
- the masks 7, 7 ' are arranged by means of the rods 8 so that the outer edges 1 1, 1 l 'of the notches 9, 9' are each placed substantially at the same distance "d" from the edge 12 of the ferrule 3 facing which they are arranged.
- This distance "d" is, initially, of the order of 5 mm when it is desired to deposit a nickel deposit 2 to 3 mm thick.
- the sides 13, 13 'of each mask 7, 7' which are pe ⁇ endicular to the ferrule 3 must in this example of implementation of the invention, have a minimum length of 50 mm. It is under these conditions that the masks 7, 7 ′ can deflect the current lines enough to homogenize their distribution as well as possible on the banks of the shell 3.
- the masks 7, 7 may be gradually removed 'of the ferrule 3 as the thickness of the nickel deposit increases. This removal can be carried out in successive stages or continuously. We can thus ensure that there will always be enough space between the mask and the deposit to allow the growth of the nickel deposit.
- the edges of the shell 3 will be coated in a homogeneous manner over a greater or lesser portion of their surface.
- the masks can be constituted differently from those which have just been given as an example, in so far as they make it possible to obtain the desired homogeneity for the thickness of the deposit.
- they instead of being constituted by tubes of square, rectangular or other section, they can consist of a plate or an assembly of plates, the surface of which facing the ferrule would preferably have the same configuration as that of the tubes of the 'example.
- this surface should preferably have two parallel edges each placed in the extension of the edge of the ferrule at the same distance "d" from the latter and connected by a wedge-shaped notch whose sides are pe ⁇ endicular the one to another.
- the invention does not exclude that, in order to further complete and refine the action of the masks, recourse is also had to thieves of current, integrated into the masks or independent of them, permanently or intermittently.
- the invention can be applied to the deposition of metals other than nickel on the shell.
- the cylinder thus coated can be used not only on a machine for continuously casting thin metal strips (of steel or another material) between two cylinders, but also on a machine for continuously casting thin bands where a rotating cylinder unique comes to lick the surface of a bath metallic (cast on a cylinder).
- it can also be applied to the coating of the casting surface of a massive cylinder where the ferrule and the core would constitute only one and the same part. It is also easy to transpose it to a case where the ferrule or the massive cylinder could be completely submerged in the electrolyte bath.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Continuous Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Prevention Of Electric Corrosion (AREA)
- Electrolytic Production Of Metals (AREA)
Description
Claims
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9607981A FR2750437A1 (fr) | 1996-06-27 | 1996-06-27 | Procede et installation de revetement electrolytique par une couche metallique de la surface d'un cylindre pour coulee continue de bandes metalliques minces |
| FR9607981 | 1996-06-27 | ||
| FR9616255 | 1996-12-31 | ||
| FR9616255A FR2750438B1 (fr) | 1996-06-27 | 1996-12-31 | Procede et installation de revetement electrolytique par une couche metallique de la surface d'un cylindre pour coulee continue de bandes metalliques minces |
| PCT/FR1997/001000 WO1997049843A1 (fr) | 1996-06-27 | 1997-06-06 | Procede et installation de revetement electrolytique par une couche metallique de la surface d'un cylindre pour coulee continue de bandes metalliques minces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0909346A1 true EP0909346A1 (fr) | 1999-04-21 |
| EP0909346B1 EP0909346B1 (fr) | 2002-09-18 |
Family
ID=26232791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97927245A Expired - Lifetime EP0909346B1 (fr) | 1996-06-27 | 1997-06-06 | Procede et installation de revetement electrolytique par une couche metallique de la surface d'un cylindre pour coulee continue de bandes metalliques minces |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US6228242B1 (fr) |
| EP (1) | EP0909346B1 (fr) |
| JP (1) | JP4308909B2 (fr) |
| KR (1) | KR100428830B1 (fr) |
| CN (1) | CN1117181C (fr) |
| AT (1) | ATE224467T1 (fr) |
| AU (1) | AU715095B2 (fr) |
| BR (1) | BR9709898A (fr) |
| CA (1) | CA2252923C (fr) |
| CZ (1) | CZ295349B6 (fr) |
| DE (1) | DE69715622T2 (fr) |
| DK (1) | DK0909346T3 (fr) |
| ES (1) | ES2183183T3 (fr) |
| FR (1) | FR2750438B1 (fr) |
| PL (1) | PL187533B1 (fr) |
| PT (1) | PT909346E (fr) |
| RO (1) | RO119204B1 (fr) |
| RU (1) | RU2188260C2 (fr) |
| SK (1) | SK283880B6 (fr) |
| TR (1) | TR199802696T2 (fr) |
| UA (1) | UA54438C2 (fr) |
| WO (1) | WO1997049843A1 (fr) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6576110B2 (en) * | 2000-07-07 | 2003-06-10 | Applied Materials, Inc. | Coated anode apparatus and associated method |
| TWI227285B (en) * | 2001-10-15 | 2005-02-01 | Univ Southern California | Methods of and apparatus for producing a three-dimensional structure |
| DE10156925A1 (de) * | 2001-11-21 | 2003-05-28 | Km Europa Metal Ag | Aushärtbare Kupferlegierung als Werkstoff zur Herstellung von Giessformen |
| TW590822B (en) * | 2001-11-21 | 2004-06-11 | Km Europa Metal Ag | Casting-roller for a two-roller-casting equipment and its manufacturing method |
| US7560015B2 (en) * | 2002-05-27 | 2009-07-14 | Concast Ag | Process for electrolytic coating of a strand casting mould |
| KR101082896B1 (ko) * | 2002-05-27 | 2011-11-11 | 에스엠에스 콘캐스트 에이지 | 연속 주조 주형의 전해 코팅 방법 |
| US20060037865A1 (en) * | 2004-08-19 | 2006-02-23 | Rucker Michael H | Methods and apparatus for fabricating gas turbine engines |
| KR100733366B1 (ko) * | 2005-12-23 | 2007-06-29 | 주식회사 포스코 | 주조용 몰드의 전해식 도금 장치 |
| US8784618B2 (en) | 2010-08-19 | 2014-07-22 | International Business Machines Corporation | Working electrode design for electrochemical processing of electronic components |
| KR101495419B1 (ko) * | 2013-04-10 | 2015-02-24 | 주식회사 포스코 | 에지 과도금을 방지하기 위한 전기도금장치 |
| CN105154961B (zh) * | 2015-10-08 | 2017-07-04 | 江苏宏联环保科技有限公司 | 高度可调节的电镀设备 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE397490A (fr) * | 1932-07-13 | |||
| GB1138561A (en) * | 1966-01-28 | 1969-01-01 | Sp Kb Tyazhelykh Tsvetnykh Met | A rotatable drum cathode having means for facilitating continuous stripping of metal foil formed by electrodeposition on the cathode |
| SU996526A1 (ru) * | 1981-09-04 | 1983-02-15 | Производственное Объединение "Днепротяжбуммаш" Им.Артема | Устройство дл электрохимической обработки деталей |
| JPH07116636B2 (ja) * | 1986-09-26 | 1995-12-13 | 川崎製鉄株式会社 | ラジアル型めつきセル |
| JP3348963B2 (ja) * | 1994-04-14 | 2002-11-20 | ディップソール株式会社 | 亜鉛−コバルト合金アルカリ性めっき浴及び該めっき浴を用いためっき方法 |
-
1996
- 1996-12-31 FR FR9616255A patent/FR2750438B1/fr not_active Expired - Fee Related
-
1997
- 1997-06-06 US US09/147,205 patent/US6228242B1/en not_active Expired - Lifetime
- 1997-06-06 DE DE69715622T patent/DE69715622T2/de not_active Expired - Lifetime
- 1997-06-06 SK SK1472-98A patent/SK283880B6/sk not_active IP Right Cessation
- 1997-06-06 PT PT97927245T patent/PT909346E/pt unknown
- 1997-06-06 ES ES97927245T patent/ES2183183T3/es not_active Expired - Lifetime
- 1997-06-06 WO PCT/FR1997/001000 patent/WO1997049843A1/fr not_active Ceased
- 1997-06-06 CA CA002252923A patent/CA2252923C/fr not_active Expired - Fee Related
- 1997-06-06 PL PL97330923A patent/PL187533B1/pl not_active IP Right Cessation
- 1997-06-06 AT AT97927245T patent/ATE224467T1/de active
- 1997-06-06 BR BR9709898A patent/BR9709898A/pt not_active IP Right Cessation
- 1997-06-06 CN CN97194984A patent/CN1117181C/zh not_active Expired - Lifetime
- 1997-06-06 DK DK97927245T patent/DK0909346T3/da active
- 1997-06-06 EP EP97927245A patent/EP0909346B1/fr not_active Expired - Lifetime
- 1997-06-06 JP JP50241798A patent/JP4308909B2/ja not_active Expired - Fee Related
- 1997-06-06 TR TR1998/02696T patent/TR199802696T2/xx unknown
- 1997-06-06 RU RU99101901/02A patent/RU2188260C2/ru not_active IP Right Cessation
- 1997-06-06 UA UA99010423A patent/UA54438C2/uk unknown
- 1997-06-06 AU AU31802/97A patent/AU715095B2/en not_active Ceased
- 1997-06-06 RO RO98-01742A patent/RO119204B1/ro unknown
- 1997-06-06 KR KR10-1998-0708772A patent/KR100428830B1/ko not_active Expired - Lifetime
- 1997-06-06 CZ CZ19984002A patent/CZ295349B6/cs not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9749843A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100428830B1 (ko) | 2004-09-18 |
| US6228242B1 (en) | 2001-05-08 |
| CZ295349B6 (cs) | 2005-07-13 |
| DK0909346T3 (da) | 2003-01-27 |
| RO119204B1 (ro) | 2004-05-28 |
| KR20000010694A (ko) | 2000-02-25 |
| SK283880B6 (sk) | 2004-04-06 |
| SK147298A3 (en) | 1999-06-11 |
| EP0909346B1 (fr) | 2002-09-18 |
| WO1997049843A1 (fr) | 1997-12-31 |
| BR9709898A (pt) | 1999-08-10 |
| TR199802696T2 (xx) | 1999-03-22 |
| FR2750438B1 (fr) | 1998-08-07 |
| RU2188260C2 (ru) | 2002-08-27 |
| ES2183183T3 (es) | 2003-03-16 |
| AU715095B2 (en) | 2000-01-13 |
| FR2750438A1 (fr) | 1998-01-02 |
| ATE224467T1 (de) | 2002-10-15 |
| JP4308909B2 (ja) | 2009-08-05 |
| JP2000512556A (ja) | 2000-09-26 |
| UA54438C2 (uk) | 2003-03-17 |
| CZ400298A3 (cs) | 1999-03-17 |
| CN1117181C (zh) | 2003-08-06 |
| CN1219983A (zh) | 1999-06-16 |
| AU3180297A (en) | 1998-01-14 |
| CA2252923C (fr) | 2005-09-20 |
| DE69715622D1 (de) | 2002-10-24 |
| PL330923A1 (en) | 1999-06-07 |
| PT909346E (pt) | 2003-09-30 |
| DE69715622T2 (de) | 2003-08-07 |
| PL187533B1 (pl) | 2004-07-30 |
| CA2252923A1 (fr) | 1997-12-31 |
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