EP0355628B1 - Procédé pour décontaminer chimiquement la surface d'un élément de construction métallique d'une installation de réacteur nucléaire - Google Patents

Procédé pour décontaminer chimiquement la surface d'un élément de construction métallique d'une installation de réacteur nucléaire Download PDF

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Publication number
EP0355628B1
EP0355628B1 EP89114917A EP89114917A EP0355628B1 EP 0355628 B1 EP0355628 B1 EP 0355628B1 EP 89114917 A EP89114917 A EP 89114917A EP 89114917 A EP89114917 A EP 89114917A EP 0355628 B1 EP0355628 B1 EP 0355628B1
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EP
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Prior art keywords
acid
process according
aqueous solution
decontamination
solution contains
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Expired - Lifetime
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EP89114917A
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German (de)
English (en)
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EP0355628A1 (fr
Inventor
Rainer Dr. Gassen
Klaus Dipl.-Ing. Zeuch (Fh)
Horst-Otto Bertholdt
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Areva GmbH
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Siemens AG
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
    • G21F9/004—Decontamination of the surface of objects with chemical or electrochemical processes of metallic surfaces

Definitions

  • the invention relates to a method for chemical decontamination of the surface of a metallic component of a nuclear reactor plant.
  • radioactive oxide layers must be removed from the surfaces of the components to be treated or tested.
  • a suitable method with chemical decontamination is known for example from German patent specification 26 13 351. In the known method, decontamination takes place in two steps or stages. First, an oxidative treatment with alkaline permanganate solution is carried out as a first step. The second step involves contacting the components with a citrate oxalate solution, in which an essential component is oxalic acid.
  • decontamination processes also run in two stages, with oxalic acid always being used to detach deposits, in particular to detach oxide deposits.
  • Known decontamination processes see e.g. B. as a first stage oxidation with manganese acid (HMnO4), with nitric acid (HNO3) in conjunction with potassium permanganate (KMnO4) or with sodium hydroxide (NaOH) in combination with potassium permanganate (KMnO4) before.
  • HNO3 manganese acid
  • KMnO4 nitric acid
  • NaOH sodium hydroxide
  • the oxides are then detached from the surface to be decontaminated; complexing organic acids are used as reducing agents, and often only oxalic acid is used.
  • a mixture of different acids is used, in which oxalic acid always forms an essential component.
  • oxalic acid in a decontamination process is disadvantageous for the success of the process.
  • Oxalic acid for example, causes an intergranular attack on sensitized materials, for example in the area of a weld.
  • the use of oxalic acid in the presence of heavy metals leads to the precipitation of heavy metal oxalates.
  • oxalates of manganese, cobalt, nickel and iron can fail. Since the metals mentioned contain radioactive isotopes, the precipitation of the oxalates leads to a new contamination of the surfaces of the components during the decontamination process. So there is a so-called recontamination.
  • the likelihood of recontamination is particularly high if the components to be decontaminated are made of nickel-based alloys, such as Inconel 600.
  • the components and systems to be decontaminated in a nuclear reactor plant generally consist of different materials. As a result, different oxides can also be removed with the decontamination process. Compared to a specific decontamination process, each oxide type shows a specific dissolution behavior.
  • a component for example a pump housing, which consists of two different materials, such as a nickel-based material and an iron-based material, cannot be optimally decontaminated with any of the known decontamination processes, which always use oxalic acid, with a one-time sequence of the two cleaning steps. Rather, a separate, specific decontamination process is usually necessary for each material on the component.
  • the invention has for its object to provide a cost-effective method for chemical decontamination of the surface of a metallic component of a nuclear reactor plant, which excludes recontamination by precipitation, which does not attack sensitized materials, for example in the area of weld seams, and on all materials used for the metallic components to be decontaminated are usually achieved with an equivalent good decontamination success.
  • components that are made up of several materials should also be able to be completely decontaminated.
  • the object is achieved according to the invention in that the surface is treated in a one-step process with an aqueous solution which is free from the carboxylic acid oxalic acid and contains another carboxylic acid which is converted into a further carboxylic acid by a chemical or thermal process.
  • This conversion can take place directly in the aqueous solution which is intended for the treatment of the surface. However, the conversion can also take place in a process step preceding the actual decontamination.
  • a conversion of a carboxylic acid into another carboxylic acid the advantage is achieved that, starting from an inexpensive carboxylic acid, a carboxylic acid can be obtained which ensures very good decontamination success, but which would be difficult to obtain commercially since it is either not available or very expensive is.
  • the method according to the invention also has the advantage that recontamination is avoided.
  • Heavy metal salts of carboxylic acids other than oxalic acid are much more soluble than oxalates.
  • the fact that only oxalic acid takes the place of oxalic acid in the process according to the invention prevents recontamination of the surfaces. It is essential not only to use carboxylic acids other than oxalic acid, but also to completely dispense with the smallest amount of carboxylic acid oxalic acid in the aqueous solution.
  • Carboxylic acids other than oxalic acid are able to dissolve iron oxides and also nickel oxides and, which is essential, to keep them in solution. These can then be easily removed.
  • the method according to the invention achieves the advantage that sensitized materials are not attacked intercrystalline.
  • a further major advantage is the fact that the so-called "decontamination factor" when using the method according to the invention is significantly higher than with chemical decontamination with oxalic acid.
  • the "decontamination factor” is the quotient of the dose rate of a component to be decontaminated before the treatment and the dose rate of the same component after the treatment.
  • the advantage of the method according to the invention is achieved that far higher decontamination factors are achieved than would be possible using oxalic acid, without the risk of recontamination due to the precipitation of previously detached radioactive nuclides on the cleaned metal surface.
  • the method according to the invention can be used with the same success in all materials used in the nuclear field, components and systems consisting of several materials can advantageously also be decontaminated, such as a pump housing which partly consists of an iron-based material and partly of a nickel-based material.
  • a pump housing which partly consists of an iron-based material and partly of a nickel-based material.
  • large decontamination factors are also achieved with the method according to the invention on components consisting of only one material. While only one decontent factor 140 could be achieved with the carboxylic acid oxalic acid in one test series under the same conditions, other carboxylic acids, namely dihydroxy tartaric acid in combination with pyridine-2,6-dicarboxylic acid, led to a decontent factor 650.
  • the fact that the method according to the invention is a one-step process achieves the advantage that intermediate steps, such as rinsing steps, which would be necessary in a multi-step process, can be omitted. So you come with one short decontamination time.
  • the surface of the component to be decontaminated is treated, for example, with an aqueous solution which contains at least one ketocarboxylic acid.
  • the solution can contain at least one hydroxycarboxylic acid or a mixture of at least one ketocarboxylic acid and at least one hydroxycarboxylic acid.
  • a particularly suitable ketocarboxylic acid is mesoxalic acid.
  • Particularly suitable hydroxycarboxylic acids are tartronic acid and dihydroxy tartaric acid.
  • At least one complexing agent can advantageously be added to the aqueous solution. This significantly improves the decontamination effect of ketocarboxylic acids and hydroxycarboxylic acids.
  • a suitable complexing agent is a chelating agent, such as, for example, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) and nitrilotriacetic acid (NTA), or else a pyridinecarboxylic acid, such as, for example, 2-picolinic acid or dipicolinic acid.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • NTA nitrilotriacetic acid
  • a pyridinecarboxylic acid such as, for example, 2-picolinic acid or dipicolinic acid.
  • a particularly good decontamination result is achieved, for example, after alkaline preoxidation with a ketocarboxylic acid or a hydroxycarboxylic acid, if this is combined with a pyridine carboxylic acid as a complexing agent.
  • the decontamination factors then achieved are greater than 100. Decontamination factors up to 650 are achieved.
  • Tables 1 and 2 use examples for the decontamination of austenitic CrNi steel and for the decontamination of a nickel alloy to give decontamination factors that can be achieved when using the decontamination solutions according to the invention and for comparison when using oxalic acid.
  • the aqueous solution can contain, for example, hydrogen peroxide or hypophosphite. This advantageously increases the rate of dissolution of different oxide forms in the decontamination solution.
  • Tartronic acid can only be stored refrigerated at temperatures between 0 ° C and 4 ° C.
  • tartronic acid is very expensive. It is therefore envisaged, for example, that a solution containing easily stored dihydroxy tartaric acid is brought into contact with the surface to be decontaminated, and that this solution is then heated to form tartronic acid. With certain materials, better decontamination is achieved with tartronic acid than with dihydroxy tartaric acid. The advantage is achieved that tartronic acid is produced directly in the decontamination solution from easily stored dihydroxy tartaric acid.
  • the tartronic acid can also be formed from dihydroxy tartaric acid in a process step preceding the decontamination.
  • the tartronic acid thus formed is then used for decontamination.
  • dihydroxy tartaric acid In contrast to tartronic acid, dihydroxy tartaric acid is easy to store, but it is hardly available commercially.
  • the dihydroxy tartaric acid is therefore preferably prepared from its salts, in particular from its sodium salt, which is readily and inexpensively available.
  • Mesoxalic acid can also be prepared from its salts, in particular from its sodium salt.
  • the acids mentioned are prepared from their salts by ion exchange.
  • Mesoxalic acid can also be obtained from tartronic acid instead of from its salts.
  • hydrogen peroxide is added to the aqueous decontamination solution, which contains tartronic acid, which can already be made from dihydroxy tartaric acid, which leads to the formation of mesoxalic acid from the tartronic acid.
  • This has the advantage that the mesoxalic acid is also obtained from a salt of dihydroxy tartaric acid.
  • the dihydroxy tartaric acid made from its salt is heated to give tartronic acid. This is then added with hydrogen peroxide, which leads to the formation of mesoxalic acid.
  • mesoxalic acid from tartronic acid and hydrogen peroxide can, for example, also take place in a separate container, after which the mesoxalic acid formed is introduced into the decontamination solution.
  • a solution is brought into contact with the surfaces to be decontaminated, which contains dihydroxy tartaric acid, which is produced from an inexpensive salt of this acid.
  • the solution is then heated to form tartronic acid.
  • Hydrogen peroxide is then added to the solution to form mesoxalic acid from the tartronic acid.
  • mesoxalic acid is advantageously formed in the decontamination solution from an inexpensive substance, such as the sodium salt of dihydroxy tartaric acid.
  • Suitable acids to replace the oxalic acid are also hydroxyacetic acid and ketoacetic acid.
  • Hydroxyacetic acid can be formed from tartronic acid by heating.
  • Ketoacetic acid can be formed from either mesoxalic acid by heating or by adding hydrogen peroxide from hydroxyacetic acid.
  • the treatment of the surface with the aqueous decontamination solution can be preceded by an oxidation step which is carried out in an acidic or alkaline medium.
  • This oxidation step takes place, for example, in the presence of permanganate. With this preliminary stage, the success of decontamination is increased.
  • the treatment of the surface with the aqueous decontamination solution can also be preceded by several oxidation steps, alternately in the acidic and in the alkaline medium.
  • the oxidation solutions present after the oxidation step which contain, for example, permanganate, can be destroyed and neutralized with a supplied carboxylic acid, which can be part of the aqueous decontamination solution.
  • a supplied carboxylic acid which can be part of the aqueous decontamination solution.
  • the acidic or alkaline oxidation solutions mentioned can be destroyed by mesoxalic acid or by tartronic acid. Oxalic acid is not required to reduce the permanganate.
  • the decontamination solution which may contain radioactive substances, is preferably fed to an evaporator. There the volume of the solution to be disposed of is reduced.
  • the solution to be disposed of can also be fed to an ion exchanger in which radioactive ions are retained.
  • Dicarboxylic acids still contained in the solution to be disposed of are thermally broken down to monocarboxylic acids, for example.
  • An evaporator is usually used for this.
  • the decontamination solution can be pumped around the system via a cleaning device to increase the decontamination effect during the treatment of the surface of the metallic component that is part of the system.
  • a cleaning device can be the primary circuit, but also the auxiliary system of a nuclear reactor plant.
  • a single component such as a pump housing
  • this is inserted into a container of a decontamination system.
  • the decontamination system has a pump and a cleaning device which are connected by lines and form a circuit. The decontamination solution is pumped around in this system.
  • the cleaning device is, for example, an ion exchanger or a filter.
  • the cleaning device is arranged in a bypass line that is only opened during the decontamination process.
  • Suitable devices for carrying out the method according to the invention such as the decontamination system mentioned, are known per se.
  • the method according to the invention for the chemical decontamination of surfaces has the particular advantage that a high decontamination factor is achieved without using oxalic acid can be.
  • even heavy metal salts are kept in solution, which prevents recontamination of the surfaces with precipitated salts, which may contain radioactive isotopes.
  • the acids used according to the invention there is no intercrystalline change in sensitized materials, for example in the welding area.
  • the method according to the invention is characterized in that even components which consist of several different metals can be decontaminated with good success.
  • the process according to the invention achieves equally good results for all materials used in nuclear reactor plants, for example for chromium-nickel steel, chromium steels and nickel alloys.
  • Mesoxalic acid 3 is obtained from the sodium salt 1 of mesoxalic acid 2 by ion exchange.
  • 5 dihydroxy tartaric acid 6 is obtained from the sodium salt 4 of dihydroxy tartaric acid by ion exchange.
  • Tartronic acid 8 is obtained from the dihydroxy tartaric acid 6 by thermal conversion 7.
  • Mesoxalic acid 3 can be produced from tartronic acid 8 by reaction 9 with added hydrogen peroxide.
  • Hydroxyacetic acid 11 can also be obtained from the tartronic acid 8 by thermal conversion 10.
  • Ketoacetic acid 12 can be obtained from mesoxalic acid 3 by thermal conversion 14. This can also be prepared from hydroxyacetic acid 11 by reaction 13 with added hydrogen peroxide.

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  • Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (30)

  1. Procédé de décontamination chimique de la surface d'un élément métallique d'une installation de réacteur nucléaire, caractérisé en ce qu'il consiste à traiter la surface dans un procédé en un seul stade par une solution aqueuse qui est exempte de l'acide carboxylique qu'est l'acide oxalique et qui contient un acide carboxylique différent (3, 6, 8, 11, 12) se transformant en un autre acide carboxylique (3, 8, 11, 12) par un processus (7, 9, 10, 13, 14) chimique ou thermique.
  2. Procédé suivant la revendication 1,
       caractérisé en ce que la solution aqueuse contient un acide cétocarboxylique (3).
  3. Procédé suivant la revendication 2,
       caractérisé en ce que la solution aqueuse contient l'acide mésoxalique (3).
  4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que la solution aqueuse contient un acide hydroxycarboxylique (6, 8, 11, 12).
  5. Procédé suivant la revendication 4,
       caractérisé en ce que la solution aqueuse contient de l'acide dihydroxytartrique (6).
  6. Procédé suivant l'une des revendications 4 ou 5,
       caractérisé en ce que la solution aqueuse contient de l'acide tartronique (8).
  7. Procédé suivant l'une des revendications 1 à 6,
       caractérisé en ce que la solution aqueuse contient un agent complexant.
  8. Procédé suivant la revendication 7,
       caractérisé en ce que la solution aqueuse contient, comme agent complexant, un acide pyridine carboxylique.
  9. Procédé suivant l'une des revendications 7 ou 8,
       caractérisé en ce que la solution aqueuse contient, comme agent complexant, de l'acide éthylènediaminetétracétique (EDTA).
  10. Procédé suivant l'une des revendications 1 à 9,
       caractérisé en ce que la solution aqueuse contient de l'eau oxygénée ou de l'hypophosphite.
  11. Procédé suivant l'une des revendications 5 à 10,
       caractérisé en ce qu'il consiste à mettre la surface en contact avec une solution aqueuse qui contient de l'acide dihydroxytartrique (6), puis à chauffer la solution pour former de l'acide tartronique (8).
  12. Procédé suivant l'une des revendications 6 à 11,
       caractérisé en ce que la solution aqueuse contient de l'acide tartronique (8) formé au préalable par chauffage à partir de l'acide dihydroxytartrique (6).
  13. Procédé suivant l'une des revendications 5 à 12,
       caractérisé en ce qu'il consiste à préparer l'acide dihydroxytartrique (6) à partir de l'un de ses sels, notamment de son sel de sodium (4).
  14. Procédé suivant l'une des revendications 3 à 13,
       caractérisé en ce qu'il consiste à préparer l'acide mésoxalique (3) à partir de l'un de ses sels, notamment de son sel de sodium (1).
  15. Procédé suivant l'une des revendications 13 ou 14,
       caractérisé en ce qu'il consiste à préparer l'acide (3, 6) à partir de l'un de ses sels (1,4) par échange d'ion.
  16. Procédé suivant l'une des revendications 6 à 15,
       caractérisé en ce qu'il consiste à mettre les surfaces en contact avec une solution aqueuse qui contient l'acide tartronique (8), et à ajouter (9) à la solution de l'eau oxygénée pour former de l'acide mésoxalique (3).
  17. Procédé suivant l'une des revendications 3 à 16,
       caractérisé en ce que la solution aqueuse contient de l'acide mésoxalique (3) formé au préalable par une réaction de l'acide tartronique (8) et de l'eau oxygénée.
  18. Procédé suivant l'une des revendications 5 à 17,
       caractérisé en ce qu'il consiste à mettre les surfaces en contact avec une solution aqueuse qui contient de l'acide hydroxytartrique (6), à chauffer (7) ensuite la solution aqueuse pour former de l'acide tartronique (8) et à ajouter (9) ensuite à la solution l'eau oxygénée pour former de l'acide mésoxalique (3).
  19. Procédé suivant l'une des revendications 1 à 18,
       caractérisé en ce qu'il consiste à faire précéder le traitement de la surface par la solution aqueuse d'un stade d'oxydation effectué dans un milieu acide ou alcalin.
  20. Procédé suivant la revendication 19,
       caractérisé en ce qu'il consiste à effectuer le stade d'oxydation en présence du permanganate.
  21. Procédé suivant l'une des revendications 19 ou 20,
       caractérisé en ce qu'il consiste à faire précéder le traitement des surfaces par la solution aqueuse de plusieurs stades d'oxydation, alternativement dans un milieu acide et dans un milieu alcalin.
  22. Procédé suivant l'une des revendications 19 à 21,
       caractérisé en ce qu'il consiste, après avoir effectué le stade d'oxydation, à détruire et à neutraliser la solution d'oxydation par un acide carboxylique (3, 6, 8, 11, 12) qui fait partie de la solution aqueuse de décontamination.
  23. Procédé suivant l'une des revendications 1 à 22,
       caractérisé en ce qu'il consiste à envoyer, après le traitement de la surface de l'élément métallique, la solution contenant des substances radioactives à un évaporateur.
  24. Procédé suivant l'une des revendications 1 à 22,
       caractérisé en ce qu'il consiste, après le traitement de la surface de l'élément métallique, à envoyer la solution contenant les substances radioactives à un échangeur d'ion.
  25. Procédé suivant la revendication 23,
       caractérisé en ce qu'il consiste à décomposer thermiquement en acide monocarboxylique (11, 12) dans l'évaporateur, les acides dicarboxyliques (3, 6, 8) contenus dans la solution.
  26. Procédé suivant l'une des revendications 1 à 25,
       caractérisé en ce qu'il consiste, pendant le traitement de la surface de l'élément métallique, qui fait partie du système décontaminé, à remettre en circulation par pompage la solution aqueuse dans le système avec passage dans une installation d'épuration.
  27. Procédé suivant l'une des revendications 1 à 25,
       caractérisé en ce qu'il consiste, pendant le traitement de la surface de l'élément métallique, qui est mis dans une cuve d'un système de décontamination, à remettre en circulation par pompage la solution aqueuse, dans le système de décontamination avec passage dans une installation d'épuration.
  28. Procédé suivant l'une des revendications 26 ou 27,
       caractérisé en ce que l'installation d'épuration est un échangeur d'ions.
  29. Procédé suivant l'une des revendications 26 à 28,
       caractérisé en ce que l'installation d'épuration est un filtre.
  30. Procédé suivant l'une des revendications 26 à 29,
       caractérisé en ce qu'il consiste à disposer l'installation d'épuration dans un conduit de dérivation du système ou du système de décontamination.
EP89114917A 1988-08-24 1989-08-11 Procédé pour décontaminer chimiquement la surface d'un élément de construction métallique d'une installation de réacteur nucléaire Expired - Lifetime EP0355628B1 (fr)

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DE3828727 1988-08-24
DE3828727 1988-08-24

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EP0355628B1 true EP0355628B1 (fr) 1993-11-10

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US (1) US5045273A (fr)
EP (1) EP0355628B1 (fr)
JP (1) JP2587023B2 (fr)
KR (1) KR900003911A (fr)
BR (1) BR8904236A (fr)
CA (1) CA1321128C (fr)
DE (1) DE58906153D1 (fr)
ES (1) ES2045298T3 (fr)
RU (1) RU1830149C (fr)
UA (1) UA11243A (fr)

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US6295514B1 (en) 1996-11-04 2001-09-25 3-Dimensional Pharmaceuticals, Inc. Method, system, and computer program product for representing similarity/dissimilarity between chemical compounds
US7039621B2 (en) 2000-03-22 2006-05-02 Johnson & Johnson Pharmaceutical Research & Development, L.L.C. System, method, and computer program product for representing object relationships in a multidimensional space
US7054757B2 (en) 2001-01-29 2006-05-30 Johnson & Johnson Pharmaceutical Research & Development, L.L.C. Method, system, and computer program product for analyzing combinatorial libraries
US7117187B2 (en) 1996-11-04 2006-10-03 Johnson & Johnson Pharmaceutical Reseach & Develpment, L.L.C. Method, system and computer program product for non-linear mapping of multi-dimensional data
US7139739B2 (en) 2000-04-03 2006-11-21 Johnson & Johnson Pharmaceutical Research & Development, L.L.C. Method, system, and computer program product for representing object relationships in a multidimensional space
US7416524B1 (en) 2000-02-18 2008-08-26 Johnson & Johnson Pharmaceutical Research & Development, L.L.C. System, method and computer program product for fast and efficient searching of large chemical libraries
WO2013041595A1 (fr) 2011-09-20 2013-03-28 Nis Ingenieurgesellschaft Mbh Procédé de dégradation d'une couche d'oxyde
DE102013102331B3 (de) * 2013-03-08 2014-07-03 Horst-Otto Bertholdt Verfahren zum Abbau einer Oxidschicht
WO2018149862A1 (fr) 2017-02-14 2018-08-23 Siempelkamp NIS Ingenieurgesellschaft mbH Procédé de décomposition d'une couche d'oxyde contenant des radionucléides

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US5200117A (en) * 1989-04-03 1993-04-06 Mobil Oil Corporation Sulfate scale dissolution
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JP2587023B2 (ja) 1997-03-05
ES2045298T3 (es) 1994-01-16
RU1830149C (ru) 1993-07-23
BR8904236A (pt) 1990-04-10
EP0355628A1 (fr) 1990-02-28
CA1321128C (fr) 1993-08-10
UA11243A (uk) 1996-12-25
DE58906153D1 (de) 1993-12-16
US5045273A (en) 1991-09-03
KR900003911A (ko) 1990-03-27

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