EP0602437B1 - Installation de décapage et procédé d'exploitation de l'installation - Google Patents
Installation de décapage et procédé d'exploitation de l'installation Download PDFInfo
- Publication number
- EP0602437B1 EP0602437B1 EP93119150A EP93119150A EP0602437B1 EP 0602437 B1 EP0602437 B1 EP 0602437B1 EP 93119150 A EP93119150 A EP 93119150A EP 93119150 A EP93119150 A EP 93119150A EP 0602437 B1 EP0602437 B1 EP 0602437B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pickling
- tanks
- strip
- tank
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000005554 pickling Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 33
- 239000007924 injection Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 31
- 230000001419 dependent effect Effects 0.000 claims 1
- 230000006978 adaptation Effects 0.000 abstract description 4
- 238000011144 upstream manufacturing Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 15
- 239000007921 spray Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000003903 pelvic floor Anatomy 0.000 description 1
- 210000004197 pelvis Anatomy 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G3/00—Apparatus for cleaning or pickling metallic material
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
- C23G3/024—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by a combination of dipping and spraying
Definitions
- the invention relates to a method for operating a pickling system for pickling rolled strips in, in particular, a plurality of pickling tanks arranged one behind the other and filled with an acid-containing pickling medium, through which the strip is moved, and into those arranged at least laterally above and below the strip running level on the pool An acidic pickling medium is injected into the injection nozzles, and a pickling system for carrying out the process.
- a pickling line with side nozzles above and below the strip running plane has become known from US-A-2 418 386.
- the surface of the strip Before further processing of rolled strips, the surface of the strip must be free of scale.
- the scale is produced as a so-called secondary scale as it passes through the hot strip finishing line, on the cooling roller table and also partially in the coiler where the strips are wound into coils or coils.
- the scale achieves a different layer thickness and a different chemical structure.
- Acid pickling of this type can consist of several flat pickling tanks arranged one behind the other, which are operated with, for example, 18% preheated hydrochloric acid.
- the belt is pulled or pushed through the pickling tanks, whereby the scale layer dissolves in the acid.
- the acid itself depletes in its concentration during the pickling process, so that the continuous supply of fresh acid is required.
- the acid is introduced into the last pickling tank. This is intended to give the surface of the strip the final treatment before leaving the stain.
- the pickling agent is pumped from the last basin in countercurrent to the upstream basin, so that the acid reaches the basin further ahead with decreasing concentration.
- the invention is therefore based on the object of providing a method and a device with which the operation of a generic pickling system can be improved, in particular a flexible adaptation to the respective pickling task with the aim of reducing the pickling time.
- This object is achieved in a method of the type mentioned in that the lateral injections are controlled variably and the pickling medium is injected with a preselectable amount per injection, the media temperature and / or the acid concentration and / or the nozzle outlet speed of the pickling medium being preselectable or . are.
- the invention is based on the knowledge gained from the long-term operation of such systems that a significant potential of possible measures has so far remained unused to reduce the pickling time. This potential lies in the chemical reaction between the scale layer and the pickling agent, which takes place at different speeds, depending on the material quality, the scale layer thickness and the scale structure, the iron content of the pickling agent, the acid content and the temperature of the pickling medium.
- the inventive selective activation and variable control of the preferably lateral injections into the individual pools with any preselectable amount of the injected pickling medium achieves an optimized swirling on the top and bottom of the strip, with the result that the predetermined acid concentration is established in the boundary layer.
- the pickling medium is preferably transferred from one tank to another tank according to process-related requirements, whereby preferably the injected quantities of the pickling medium and / or the transfer strategy can be preset and selected with the help of a process computer forth, preferably at several points along the length of the pickling tank, and the strategy for pumping around the pickling agent from one to the other tank to achieve an optimal adaptation of the operation of the pickling system to the respective pickling task.
- the conditions resulting from the combination of material quality, scale layer thickness and structure are regarded as pickling tasks.
- the measures according to the invention thus allow the pickling line to be preset as a function of the pickling task. They enable flexible adaptation to the respective pickling task and lead to a reduction in the pickling time and avoid over-pickling.
- the actuators required for this are provided according to the invention in that on both sides of the pool (s) above and below the belt running level, variably controllable injections are arranged in front of or behind floor sliding blocks in the pool and integrated switching valves in the piping of a pump system connected to the pool or pools are, wherein the pump system is advantageously connected to the process computer controlling the switching valves.
- the piping which is thus useful and has integrated switching valves, different strategies can be implemented to master the pickling task, for example the amount and intensity of the pickling medium supplied can be varied.
- the injections can be advantageous over the length of the pelvis alternately offset and / or alternately above and below the belt level. It is recommended that a double injection with opposing spray nozzles is arranged at least on the outlet side of the basin or basins. Double injection means that there is both a lower and an upper injection on each side and the two injections are in the same plane.
- the injections can be arranged at a distance of 0 to 2000 mm in front of or behind the floor sliding blocks.
- the floor sliding blocks which are arranged transversely to the belt running direction, support the belt downwards on the one hand and, on the other hand, serve to mix the pickling medium, which is further supported by the arrangement of the injections found at a distance from the floor sliding blocks. Because in the area of the floor sliding stones, there are no longer any dead zones with low-acid treatment liquid, rather the bath liquid is also mixed and whirled there vigorously.
- the double injection which is arranged at least on the outlet side of the basin or basins, causes a strong turbulence, since the aligned opposite liquid jets complement each other in the turbulence of the treatment liquid and ensure a uniform temperature or temperature compensation.
- Additional switching valves enable different transfer strategies for transferring the pickling medium from one tank to the other tank. These consist essentially in the fact that the transfer of the basins can be carried out in synchronism with the direction of travel of the belt, in an opposite direction or as a combination of the same and the opposite direction.
- the pickling task is to be optimally solved with the selected strategy.
- the acid is introduced into the first tank and passed on to the subsequent tank at the end of the tank.
- the pre-setting of the transfer strategy including the injection of acid can also be carried out manually, based on the experience gained, however the use of a process computer is recommended.
- FIG. 1 Only one basin 2 of a pickling plant 1 is shown in FIG. 1; The basin 2 can be followed by further basins, each filled with a pickling medium up to the liquid level 3.
- a e.g. strip 4 rolled in a hot strip finishing mill is moved through the basin 2 in the direction of arrow 5 by means not shown, e.g. pulled or pushed.
- the belt 4 is supported on floor sliding blocks 6, which are arranged at a distance from one another on the pelvic floor transversely to the belt running direction 5.
- the left end of the basin 2 is provided below the band 4 in the side walls 7 (see FIG. 3) provided inlets 8 opposite one another in alignment.
- Double injections 9 are then arranged towards the outlet side.
- These consist of spray nozzles 10 arranged on both sides of the basins 2, both above and below the belt running level, which inject fresh acid into the liquid bath.
- Fresh acid is also introduced via supply pipes 11 with distributor nozzles 12 which are laid on the inlet and outlet sides above the liquid level 3.
- the nozzles 12 are aligned in such a way that the inlet-side distributor nozzles 12 in and the outlet-side distributor nozzles 12 are directed against the surface of the belt 4 counter to the direction of belt travel 5.
- the basin 102 of a pickling system 100 shown in FIGS. 2 to 4 differs from the embodiment according to FIG. 1 only in a different arrangement of the injections 8, so that corresponding components are provided with the same reference numbers.
- the injections 8 are arranged alternately above and below the band 4, but without being offset in the longitudinal direction, which would also be a possible variant. How out 3 results, is located in the right side wall 7 of the basin 102 in the direction of travel 5, first one above, then one below (cf.
- the nozzles 8 are connected via pipes 14 to a pump system 15 which feeds fresh acid from the storage tank 16 via the pipes 14 and the spray nozzles 10 or nozzles 8, 9 into the bath liquid.
- Controllable switching valves 17 integrated in the pipelines are assigned to the injections, which allow selective activation of the spray nozzles 10 and variations in the amount of acid injected.
- the pump system 15 is - as indicated in FIGS. 1 and 2 by dashed control lines - connected to a process computer 18 shown as a black box.
- the pipes 14 connected to the process computer 18 via the pump system 15 and having the integrated switching valves 17 thus enable the selective activation of the spray nozzles 10.
- the transfer is also possible of the pickling medium from one basin to the other basin according to different strategies, which are based on whether the transfer of the basin should be carried out in synchronism with the direction 5 of the belt 4, in the opposite direction or as a combination of both.
- the presetting of the pickling plant 1, 100 to the desired transfer strategy and the pickling task to be carried out ensure that the entire length of the pickling plant 1, 100 adapted to the respective requirements, constant overall level of the acid concentration in the individual basins 2 and reduce the depletion of acid concentration in the boundary layer between the surfaces of the belt 4 and the pickling medium and the dead zones in the area in particular of the bottom sliding blocks 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Details Or Accessories Of Spraying Plant Or Apparatus (AREA)
- ing And Chemical Polishing (AREA)
- Meat, Egg Or Seafood Products (AREA)
Claims (10)
- Procédé pour le fonctionnement d'une installation de décapage (1, 100) pour le décapage de bandes laminées (4) dans en particulier plusieurs bassins de décapage (2, 102) placés les uns derrière les autres et remplis d'un agent de décapage contenant un acide, à travers lesquels on fait passer la bande (4) et dans lesquels on injecte un agent de décapage contenant un acide via des injecteurs (8, 9, 10) disposés au moins latéralement sur les bassins (2, 102), au-dessus et au-dessous du plan de passage de la bande, caractérisé en ce que les injecteurs (9, 8, 10) sont à commande variable et en ce que, par injection, l'agent de décapage est injecté en une quantité définie choisie au préalable, la concentration en acide et/ou la température de l'agent et/ou la vitesse de sortie de l'injecteur de l'agent de décapage pouvant être choisies au préalable.
- Procédé selon la revendication 1, caractérisé en ce que l'agent de décapage est transvasé d'un bassin dans un autre bassin en fonction des données provenant du procédé.
- Procédé selon la revendication 2, caractérisé en ce que le transvasement du réservoir est réalisé en synchronisation avec la direction d'avancement de la bande (4).
- Procédé selon une quelconque des revendications 1 à 3, caractérisé en ce que les quantités injectées d'agent de décapage et/ou la stratégie de transvasement sont réglées et choisies au préalable à l'aide d'un ordinateur industriel.
- Installation de décapage (1, 100) pour le décapage de bande laminées (4) dans en particulier plusieurs bassins de décapage (2, 102) placés les uns derrière les autres et remplis d'un agent de décapage contenant un acide, à travers lesquels on fait passer la bande (4) et dans lesquels on injecte un agent de décapage contenant un acide via des injecteurs (8, 9, 10) disposés au moins latéralement sur les bassins (2, 102), en particulier pour la réalisation du procédé selon une quelconque des revendications 1 à 4, caractérisée en ce que les injections (8, 9, 10) à commande variable présentes des deux côtés du bassin ou des bassins (2, 102), au-dessus et au-dessous du plan de passage de la bande, sont disposées devant ou derrière des têtes coulissantes (6) situées sur le fond dans le bassin ou les bassins (2, 102) et en ce qu'on a intégré des soupapes de commande (17) dans la tuyauterie (14) d'un système de pompage (15) raccordé au bassin ou aux bassins (2, 102).
- Installation de décapage selon la revendication 5 ou 6, caractérisée en ce que les injections (8, 9, 10) sont disposées à une distance comprise entre 0 et 2000 mm devant ou derrière les têtes coulissantes (6) du fond.
- Installation de décapage selon la revendication 5 ou 6, caractérisée en ce qu'au moins une double injection (9) située du côté de la sortie du bassin ou des bassins (2, 102) est disposée avec des gicleurs (10) opposés.
- Installation de décapage selon une quelconque des revendications 5 à 7, caractérisée par des injections (8, 9, 10) disposées de manière à ce qu'elles soient décalées alternativement sur la longueur du bassin (2, 102).
- Installation de décapage selon une quelconque des revendications 5 à 8, caractérisée en ce que les injections (8, 9, 10) sont disposées alternativement au-dessus et au-dessous du plan de passage de la bande.
- Installation de décapage selon la revendication 5, caractérisée en ce que le système de pompage (15) est raccordé à un ordinateur industriel (18).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4240572A DE4240572A1 (de) | 1992-12-03 | 1992-12-03 | Beizanlage und Verfahren zum Betreiben der Beizanlage |
DE4240572 | 1992-12-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0602437A1 EP0602437A1 (fr) | 1994-06-22 |
EP0602437B1 true EP0602437B1 (fr) | 1997-03-12 |
Family
ID=6474230
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93119150A Expired - Lifetime EP0602437B1 (fr) | 1992-12-03 | 1993-11-27 | Installation de décapage et procédé d'exploitation de l'installation |
Country Status (8)
Country | Link |
---|---|
US (1) | US5545260A (fr) |
EP (1) | EP0602437B1 (fr) |
JP (1) | JP3322965B2 (fr) |
CN (1) | CN1037706C (fr) |
AT (1) | ATE150098T1 (fr) |
DE (2) | DE4240572A1 (fr) |
ES (1) | ES2099886T3 (fr) |
RU (1) | RU2115768C1 (fr) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3404116A1 (de) * | 1984-02-07 | 1985-08-08 | Merck Patent Gmbh, 6100 Darmstadt | Stickstoffhaltige heterocyclen |
FR2721328B1 (fr) * | 1994-06-15 | 1996-09-06 | Ugine Sa | Procédé de décapage de matériaux métalliques, notamment en acier allié, en acier inoxydable ou en alliage de titane, par une solution du type contenant des ions ferriques en milieu acide. |
AT404030B (de) * | 1995-02-15 | 1998-07-27 | Andritz Patentverwaltung | Verfahren zur beize von materialien aus stahl, insbesondere edelstahl |
AT403699B (de) * | 1996-03-14 | 1998-04-27 | Andritz Patentverwaltung | Vorrichtung zum oberflächenbehandeln mit flüssigkeiten |
DE19842971A1 (de) * | 1998-09-19 | 2000-04-13 | Gewerk Keramchemie | Verfahren und Vorrichtung zum Beizen von ebenflächigem, insbesondere bandförmigem Behandlungsgut |
FR2784998B1 (fr) * | 1998-10-22 | 2001-01-12 | Kvaerner Metals Clecim | Installation de decapage d'une bande metallique |
IT1302912B1 (it) * | 1998-12-10 | 2000-10-10 | Ct Sviluppo Materiali Spa | Procedimento accelerato per il decapaggio di nastri d'acciaio edispositivo per realizzarlo. |
DE10020633A1 (de) * | 2000-04-27 | 2001-11-08 | Sms Demag Ag | Verfahren und Vorrichtung zum Behandeln der Oberfläche von metallischem Bandgut, insbesondere zum Beizen von Walzgut |
DE10021789A1 (de) * | 2000-05-10 | 2001-11-15 | Sms Demag Ag | Anlage für die Oberflächenbehandlung eines Metallstranges, insbesondere zum Beizen eines Stahlbandes |
KR100825283B1 (ko) * | 2001-12-01 | 2008-04-28 | 주식회사 포스코 | 전해청정라인에서의 냉연강판 세정장치 및 이를 이용한세정방법 |
AT413219B (de) * | 2002-09-12 | 2005-12-15 | Voest Alpine Ind Anlagen | Verfahren und vorrichtung zur oberflächenbehandlung eines metallbandes |
AT413218B (de) * | 2002-09-12 | 2005-12-15 | Voest Alpine Ind Anlagen | Verfahren und vorrichtung zur, insbesondere kontinuierlichen, oberflächenbehandlung, insbesondere zur reinigung, eines metallbandes |
US20040175252A1 (en) * | 2003-03-03 | 2004-09-09 | Kurczynski Richard J. | Fastener and washer assembly and method of forming same |
JP4658834B2 (ja) * | 2006-03-13 | 2011-03-23 | 新日本製鐵株式会社 | 噴流式酸洗設備 |
CN100434570C (zh) * | 2006-07-13 | 2008-11-19 | 山西太钢不锈钢股份有限公司 | 铬不锈钢酸洗冷却方法 |
DE102008019301B3 (de) * | 2008-04-16 | 2010-01-07 | Thyssenkrupp Steel Ag | Schubbeize zum Beizen eines Metallbands |
DE102008047029A1 (de) * | 2008-09-13 | 2010-03-18 | Sms Siemag Aktiengesellschaft | Entzunderungsvorrichtung |
CN102330100A (zh) * | 2011-07-01 | 2012-01-25 | 云南钛业股份有限公司 | 一种钛带酸洗工艺方法 |
EP3029163B9 (fr) * | 2014-12-02 | 2019-11-27 | CMI UVK GmbH | Procédé et système de traitement d'une bande d'acier au carbone, notamment pour un traitement de décapage |
CN105215855B (zh) * | 2015-08-21 | 2017-04-26 | 太原科技大学 | 利用磨料浆对金属带材进行抛、喷除鳞的装置 |
EP3385008A1 (fr) * | 2017-04-04 | 2018-10-10 | Primetals Technologies Austria GmbH | Décalamineur et procédé de décalaminage chimique d'une bande métallique |
CN109185162B (zh) * | 2018-10-25 | 2021-03-19 | 安徽众源新材料股份有限公司 | 酸泵及其铜带清洗装置 |
EP3967789A1 (fr) | 2020-09-11 | 2022-03-16 | Centre de Recherches Métallurgiques ASBL - Centrum voor Research in de Metallurgie VZW | Procédé de décapage ultrarapide et installation associée |
CN112853367B (zh) * | 2021-02-26 | 2021-08-06 | 温州宪江防腐设备有限公司 | 一种不锈钢智能酸洗工艺流水线 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE482725C (de) * | 1920-07-27 | 1929-09-30 | Peroxydwerk Siesel Akt Ges | Verfahren zum Konzentrieren von verduennten Wasserstoffsuperoxydloesungen durch Destillation im Vakuum |
US2418386A (en) * | 1942-01-17 | 1947-04-01 | Goodman Mfg Co | Continuous pickling and cleaning device for metal |
DE881657C (de) * | 1949-01-07 | 1953-07-02 | Ici Ltd | Verfahren zur Herstellung von Aminen |
NL109944C (fr) * | 1960-02-20 | |||
US3445284A (en) * | 1963-11-18 | 1969-05-20 | Dravo Corp | Process for pickling of steel strip and regeneration of the contact acid |
DE3209890C2 (de) * | 1982-03-18 | 1986-04-10 | Bwg Bergwerk- Und Walzwerk-Maschinenbau Gmbh, 4100 Duisburg | Beizanlage zum kontinuierlichen Beizen von Metallbändern |
JPS60243290A (ja) * | 1984-05-17 | 1985-12-03 | Kobe Steel Ltd | 酸洗ムラの発生を防止する長尺金属材の酸洗方法 |
JPS61235583A (ja) * | 1985-04-10 | 1986-10-20 | Sumitomo Metal Ind Ltd | 鋼帯の連続酸洗方法 |
DE3629894A1 (de) * | 1986-08-29 | 1988-03-03 | Mannesmann Ag | Anlage zur oberflaechenbehandlung von kontinuierlich durchlaufenden baendern, insbesondere beizanlage |
US4920995A (en) * | 1988-08-18 | 1990-05-01 | Continental Installers Corporation | Process for continuous strip pickling |
JP3034544B2 (ja) * | 1990-01-31 | 2000-04-17 | ヤマハ発動機株式会社 | 自動二輪車のキックペダル装置 |
DE4031234C2 (de) * | 1990-10-04 | 1994-02-03 | Gewerk Keramchemie | Verfahren und Vorrichtung zur Oberflächenbehandlung von bandförmigem Behandlungsgut |
DE4033867C2 (de) * | 1990-10-22 | 1993-11-11 | Mannesmann Ag | Verfahren zum Beizen von Bändern |
-
1992
- 1992-12-03 DE DE4240572A patent/DE4240572A1/de not_active Withdrawn
-
1993
- 1993-11-27 AT AT93119150T patent/ATE150098T1/de not_active IP Right Cessation
- 1993-11-27 DE DE59305747T patent/DE59305747D1/de not_active Expired - Fee Related
- 1993-11-27 EP EP93119150A patent/EP0602437B1/fr not_active Expired - Lifetime
- 1993-11-27 ES ES93119150T patent/ES2099886T3/es not_active Expired - Lifetime
- 1993-12-02 JP JP30293393A patent/JP3322965B2/ja not_active Expired - Fee Related
- 1993-12-02 RU RU93053904A patent/RU2115768C1/ru not_active IP Right Cessation
- 1993-12-03 CN CN93120812A patent/CN1037706C/zh not_active Expired - Fee Related
- 1993-12-03 US US08/161,838 patent/US5545260A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE59305747D1 (de) | 1997-04-17 |
CN1088631A (zh) | 1994-06-29 |
ATE150098T1 (de) | 1997-03-15 |
JPH06322568A (ja) | 1994-11-22 |
US5545260A (en) | 1996-08-13 |
JP3322965B2 (ja) | 2002-09-09 |
EP0602437A1 (fr) | 1994-06-22 |
ES2099886T3 (es) | 1997-06-01 |
DE4240572A1 (de) | 1994-06-09 |
CN1037706C (zh) | 1998-03-11 |
RU2115768C1 (ru) | 1998-07-20 |
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