EP0488423A1 - Flussmittel für die Trockenverzinkung und Verfahren zum Feuerverzinken von Stahl - Google Patents

Flussmittel für die Trockenverzinkung und Verfahren zum Feuerverzinken von Stahl Download PDF

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Publication number
EP0488423A1
EP0488423A1 EP91120665A EP91120665A EP0488423A1 EP 0488423 A1 EP0488423 A1 EP 0488423A1 EP 91120665 A EP91120665 A EP 91120665A EP 91120665 A EP91120665 A EP 91120665A EP 0488423 A1 EP0488423 A1 EP 0488423A1
Authority
EP
European Patent Office
Prior art keywords
flux
chloride
group
zinc
molten
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
Application number
EP91120665A
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English (en)
French (fr)
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EP0488423B1 (de
Inventor
Tatsumi Izeki
Yoshihiko Takano
Tetsuya Nakada
Koshi Takada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Tanaka Galvanizing Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Tanaka Galvanizing Co Ltd
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Publication date
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Publication of EP0488423A1 publication Critical patent/EP0488423A1/de
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Publication of EP0488423B1 publication Critical patent/EP0488423B1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30—Fluxes or coverings on molten baths

Definitions

  • This invention relates to a water-soluble flux which is used for the treatment of iron or steel to be coated with molten zinc, a molten alloy of zinc and aluminum, a molten alloy of zinc and aluminum further containing other elements, or molten aluminum.
  • the material to be coated is subjected to pretreatment by a process comprising the steps of degreasing, rinsing with water, pickling, rinsing with water, and flux treatment.
  • the flux treatment of the steel to be coated is usually carried out by a dry process comprising dipping it in an aqueous flux solution, and drying it, though there is also a wet process.
  • a great deal of research work has, therefore, been made to obtain a coating giving a higher degree of corrosion resistance by electroplating or molten metal coating.
  • a molten alloy of zinc and aluminum has, among others, drawn attention as being able to form a coating providing a high degree of corrosion resistance, and is already used to some extent or other for coating steel sheets. It is employed in a continuous coating process which is carried out in a non-oxidizing atmosphere.
  • a flux comprising at least one chloride selected from the group consisting of zinc chloride.
  • alkyl quaternary ammonium salt with alkyl group having 7 to 18 carbons, or an alkylamine with alkyl group having 1 to 18 carbons, or both are preferably used as the aliphatic nitrogen derivative, or derivatives.
  • the preferred alkyl quaternary ammonium salts are alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
  • the flux preferably comprises 10 to 50% by weight of at least one of zinc chloride and stannous chloride, 1 to 20% by weight of at least one of alkali metal chloride and alkaline earth metal chloride, and 0.1 to 30% by weight of at least one of alkyl quaternary ammonium salts and alkylamines.
  • This object is attained by a process comprising the steps of pretreating the steel to be coated by dipping it in an alkali bath to degrease it, rinsing it with water, and pickling it ; treating the steel by dipping with a flux containing at least one chloride selected from the group consisting of zinc chloride, stannous chloride, alkali metal chloride and alkaline earth metal chloride, and at least one aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons : dipping the steel in a bath of molten metal to form a coating on it ; and cooling the steel by dipping it in water, or by exposing it to air.
  • a flux containing at least one chloride selected from the group consisting of zinc chloride, stannous chloride, alkali metal chloride and alkaline earth metal chloride, and at least one aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons dipping the steel in a bath of molten metal to form a coating on it
  • the flux of this invention is particularly effective for the treatment of the material to be coated with molten zinc, a molten alloy of zinc and aluminum, a molten alloy of zinc and aluminum further containing other elements, or molten aluminum.
  • zinc chloride or stannous chloride dissolves the oxide which remains as a thin layer on the surface of the steel to be coated, and the oxide which forms a film on the surface of a molten bath. If the proportion of the chloride is elss than 10 % by weight, the flux does not have a satisfactory power of dissolving the oxides. If it excees 50% by weight, the flux undergoes crystallization at a low temperature and is also too viscous to use easily.
  • the alkali metal chloride, or alkaline earth metal chloride maintains the flux in a solution having an appropriate degree of viscosity at a coating temperature. If the proportion of the salt is less than 1% by weight, the flux is too low in viscosity to adhere satisfactorily to the material to be coated. If it exceeds 20% by weight, the flux is so high in viscosity that an undesirably large amount of flux adheres to the material to be coated.
  • the aliphatic nitrogen derivative bubbles on the surface of the steel dipped in a molten bath and removes the waste of the flux from the steel surface to improve the wetting of the steel surface with the molten metal.
  • a particularly strong action is exhibited by an alkyl quaternary ammonium salt, or alkylamine which bubbles as a result of Hofmann decomposition. If the proportion of the derivative is less than 0.1% by weight, the flux fails to exhibit any such action. If it exceeds 30% by weight, the flux is too expensive, and what is worse, it leaves bare spots on the steel dipped in a molten bath.
  • the flux of this invention is not only suitable for the treatment of the material to be coated with a molten alloy of zinc and aluminum, a molten alloy of zinc and aluminum further containing other elements or molten aluminum, but also it can be used for ordinary hot dip galvanizing.
  • the treatment of steel with the flux of this invention after its degreasing, rinsing with water, and pickling, enables a good coating to be formed on the steel surface by a single-stage dip-coating process where the steel to be coated is dipped directly in a molten alloy of zinc and aluminum, a molten alloy of zinc and aluminum further containing other elements or molten aluminum.
  • a single-stage dip-coating process can be employed in an ordinary hot dip galvanizing.
  • the flux of this invention essentially comprises at least one chloride selected from the group consisting of zinc chloride, stannous chloride, an alkali metal chloride and an alkaline earth metal chloride and at least one aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons.
  • the alkali metal chloride may be the chloride, such as lithium, sodium or potassium.
  • the alkaline earth metal chloride may be the chloride, such as beryllium, magnesium, calcium, strontium or barium.
  • the aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons may be an alkyl quaternary ammonium salt with alkyl group having 7 to 18 carbons, or an alkylamine with alkyl group having 1 to 18 carbons.
  • the former is preferred.
  • Preferred examples of the alkyl quaternary ammonium salts are alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
  • Examples of the alkyl groups which they may contain are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadeceny, and octadecadienyl.
  • alkylamines which can be employed are an aliphatic primary amine such as methylamine or ethylamine an aliphatic secondary amine such as dimethylamine or diethylamine, and an aliphatic tertiary amine such as trimethylamine or triethylamine.
  • the flux perferably comprises 10 to 50% by weight of zinc chloride and/or stannous chloride, 1 to 20% by weight of at least one alkali metal chloride or alkaline earth metal chloride and 0.1 to 30 % by weight of at least one alkyl quaternary ammonium salt, or alkylamine.
  • it comprises 30 to 40% by weight of zinc chloride or stannous chloride, or both, 5 to 10% by weight of at least one alkali metal chloride or alkaline earth metal chloride and 1 to 10% by weight of at least one alkyl quaternary ammonium salt, or alkylamine.
  • the flux preferably containes, for example, ZnCl2, and NaCl in a molar ratio of 4:1 and ZnCl2 and CaCl2 in a molar ratio of 3:1 if it is used for the treatment of the material to be coated in a bath having a temperature of 400 °C to 600 °C, and ZnCl2 and NaCl in a molar ratio of 3:1 and ZnCl2 and CaCl2 in a molar ratio of 2:1 if it is used for the treatment of the material to be coated in a bath having a temperature of 600 °C to 700 °C.
  • the process of this invention comprises the steps of pretreating the steel to be coated, treating it with the flux of this invention, coating it with molten metal by dipping it in a bath of the molter metal, and cooling it.
  • the process is applicable not only to large structural steel parts or members, as for towers, bridges and buildings, but also to various other materials, such as castings or forgings, steel sheets for automobiles, and wires.
  • the pretreatment of the steel to be coated is carried out by dipping it for 30 to 60 minutes in an alkali solution containing sodium hydroxide and sodium orthosilicate in a weight ratio of 1:1, having a concentration of 10 to 15%, and kept at a temperature of 60 °C to 80 °C, rinsing it with water, dipping it for 30 to 60 minutes in a 10 to 15% aqueous solution of sulfuric acid containing 0.5 to 0.7% of a pickling inhibitor, and kept at a temperature of 50 °C to 70 °C to remove scale and rust from it, and rinsing it with water, as is known in the art.
  • the flux treatment of the steel is carried out by dipping it for one or two minutes in a tank filled with the flux of this invention and heated to an appropriate temperature, which is at least 20 °C, whereby a layer of the flux is formed on the surface of the steel.
  • an appropriate temperature which is at least 20 °C
  • the flux solution can be used at ordinary temperature, it had better be heated to an appropriate temperature, so that a smaller amount of the flux solution may be carried over with the steel as treated, and so that a higher efficiency of treatment may be achieved.
  • the step of coating it is carried out by dipping it for one to 10 minutes in a bath of molten metal, such as molten zinc, a molten alloy of zinc and aluminum, a molten alloy of zinc and aluminum further containing other elements, or molten aluminum, which is held at a temperatuer of 400 °C to 700 °C, as is known in the art.
  • molten metal such as molten zinc, a molten alloy of zinc and aluminum, a molten alloy of zinc and aluminum further containing other elements, or molten aluminum, which is held at a temperatuer of 400 °C to 700 °C, as is known in the art.
  • This is a single-stage coating process.
  • the dipping time depends on the overall size and shape of the material to be coated, and the thickness of the steel, but one to 10 minutes is preferable, since a longer time of dipping results in the undesirable promotion of an alloying reaction between iron, which is the principal constituent of steel, and zinc.
  • the melting points of zinc, aluminum and an alloy of zinc and aluminum are as shown by a phase diagram in FIGURE 1, and hardly change, even if a small amount of other metal may be added.
  • the temperature of the molten bath depends on the material, construction and heat capacity of the material to be coated, though it is usually at least 10°C higher than the melting point of the metal or alloy forming the bath. After the passage of an appropriate dipping time, the steel as coated is lifted from the bath at an appropriate speed, so taht the liquid metal or alloy may be removed from it.
  • the cooling of the coated steel is carried out by dipping it in water having a temperature of 30°C to 50°C for one or two minutes, or alternatively, by exposing it to air if it is a sheet, bar, or other material having a small heat capacity.
  • a uniform and beautiful coating which is free from any bare spots, roughness, or lumpiness is formed on the steel surface.
  • FIGURE 2 is a graph showing the relation as found between the molten bath temperature and the coating weight when steel sheets each having a width of 75 mm, a length of 150 mm and a thickness of 4.2 mm and treated with the flux of this invention were coated by dipping for two minutes in a bath of a molten alloy of zinc and aluminum containing 5% of aluminum (5Al-Zn).
  • the 5Al-Zn alloy has a melting point of about 380°C, as shown in FIGURE 1. Therefore, it is theoretically possible to carry out dip coating if the molten bath has a temperature which is higher than 380 °C, and lower than the transformation temperature of iron.
  • the coating weight is, however, largely dependent or the molten bath temperature, as shown in FIGURE 2, and is too small to be industrially acceptable if the temperature is too low.
  • the temperature of 400 °C to 700 °C is, therefore, employed for the purpose of this invention.
  • the coating weight reaches the maximum range when the temperature is in the range of about 500 °C to 530 °C, as is obvious from FIGURE 2.
  • the molten bath temperature and the dipping time need, therefore, be controlled in accordance with the thickness of the coating to be formed on the steel to be coated.
  • a lustrous and smooth coating having a silver white color and free from any bare spots, or other defect could be formed on the surface of the sheet.
  • a lustrous and smooth coating having a silver white color and free from any bare spots, or other defect could be formed on the surface of the sheet.
  • the use of the flux according to this invention essentially comprising at least one chloride selected from the group consisting of zinc chloride, stannous chloride, an alkali metal chloride and an alkaline earth metal chloride and at least one aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons, enables a uniform coating giving high corrosion resistance to be formed on a steel surface from a molten alloy of zinc and aluminum by a single-stage dip-coating process without leaving any bare spots, though the single-stage process has hitherto been employed for hot dip galvanizing and considered difficult to employ for coating with a molten alloy of zinc and aluminum.
  • the flux of this invention is effective for the treatment of, among others, the material to be coated with a molten alloy of zinc and aluminum.
  • the flux of this invention is also useful for the treatment of the material to be coated with molten aluminum, for which it has been usual to employ a wet process for treatment with a flux containing fluoride, etc.
  • the flux of this invention is less likely to corrode the pot containing molten aluminum, as it consists mainly of chlorides. Moreover, the dry process improves the efficiency of the flux treatment.
  • the flux of this invention is, of course, useful for the treatment of the material to be coated with galvanizing, too. It does not undergo any substantial fuming when the material to be coated is dipped in a zinc bath, as it does not contain any ammonium chloride, unlike the conventional flux, and enables the formation of a good coating.
  • This bubbling results in the quick removal of the waste of the flux from the steel surface and the improved wetting of the steel surface with molten metal to thereby enable the formation of an improved coating adhering strongly to the steel surface.
  • a particularly good result can be achieved when the derivative is an alkyl quaternary ammonium salt, or alkylamine which bubbles as a result of Hofmann decomposition.
  • a particularly good coating can be formed when the flux comprises 10 to 50% by weight of zinc chloride or stannous chloride, or both, 1 to 20% by weight of at least one alkali metal chloride or alkaline earth metal chloride, and 0.1 to 30 % by weight of at least one alkyl quaternary ammonium salt, or alkylamine.
  • the dry process of this invention including treatment with the flux of this invention comprises the steps of pre-treating the steel to be coated by dipping it in an alkali bath to degrease it, rinsing it with water, and pickling it; treating the steel by dipping with a flux containing at least one chloride selected from the group consisting of zinc chloride, stannous chloride, an alkali metal chloride, and an alkaline earth metal chloride, and at least one aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons ; dipping said steel in a bath of molten metal to form a coating of said metal thereon ; and cooling said steel by dipping it in water, or by allowing it to cool in the air.
  • a flux containing at least one chloride selected from the group consisting of zinc chloride, stannous chloride, an alkali metal chloride, and an alkaline earth metal chloride, and at least one aliphatic nitrogen derivative with alkyl group having 1 to 18 carbons dipping said steel in
  • this process enables the manufacture of steel coated with a molten alloy of zinc and aluminum, or molten aluminum by a single dipping operation which has hitherto been considered difficult.
  • the process is, of course, useful for the manufacture of steels coated with other metals or alloys, too.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Prevention Of Electric Corrosion (AREA)
EP91120665A 1990-11-30 1991-12-02 Flussmittel zur Verwendung in einem Trockenverfahren zur Flussmittelbehandlung einer Beschichtung aus geschmolzenem Metall und Verfahren zur Herstellung von mit geschmolzenem Metall beschichtetem Stahl. Expired - Lifetime EP0488423B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2339495A JPH079056B2 (ja) 1990-11-30 1990-11-30 乾式フラックス法による溶融金属めっき用フラックス及びこのフラックスを用いた溶融金属めっき鋼材の製造方法
JP339495/90 1990-11-30

Publications (2)

Publication Number Publication Date
EP0488423A1 true EP0488423A1 (de) 1992-06-03
EP0488423B1 EP0488423B1 (de) 1998-04-01

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EP91120665A Expired - Lifetime EP0488423B1 (de) 1990-11-30 1991-12-02 Flussmittel zur Verwendung in einem Trockenverfahren zur Flussmittelbehandlung einer Beschichtung aus geschmolzenem Metall und Verfahren zur Herstellung von mit geschmolzenem Metall beschichtetem Stahl.

Country Status (7)

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EP (1) EP0488423B1 (de)
JP (1) JPH079056B2 (de)
KR (1) KR100392565B1 (de)
AU (1) AU639843B2 (de)
CA (1) CA2056666C (de)
DE (1) DE69129180T2 (de)
ES (1) ES2116991T3 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004607A1 (en) * 1993-08-05 1995-02-16 Ferro Technologies, Inc. Lead-free galvanizing technique
US7811389B2 (en) 2005-12-20 2010-10-12 Teck Metals Ltd. Flux and process for hot dip galvanization
EP2725114A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Flussmittelzusammensetzungen zur Stahlverzinkung
EP2725115A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Flussmittelzusammensetzungen zur Stahlverzinkung
EP2725117A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Kontinuierliches Einzeldip-Verfahren zur Verzinkung von langen Stahlprodukten in Zn-Al-Mg-Legierungen
EP2915607A1 (de) 2014-03-04 2015-09-09 Fontaine Holdings NV Verzinkte Metallobjekte und deren Herstellungsverfahren
EP2447389A4 (de) * 2009-06-25 2016-08-17 Nippon Steel & Sumitomo Metal Corp Hochfester zn-al-plattierter stahldraht für brücken mit ausgezeichneter korrosionsbeständigkeit und ermüdungserscheinungseigenschaften, und herstellungsverfahren dafür
CN107525739A (zh) * 2017-08-22 2017-12-29 山东交通学院 一种测定液体融雪剂最低使用温度的试验装置及试验方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW374096B (en) * 1995-01-10 1999-11-11 Nihon Parkerizing Process for hot dip-coating a steel material with a molten aluminum alloy according to an one-stage metal alloy coating method using a flux
KR100413376B1 (ko) * 2001-10-15 2004-01-03 김정섭 용융 아연 도금을 위한 플럭스 첨가제 조성물
JP7311767B2 (ja) * 2019-08-30 2023-07-20 日本製鉄株式会社 フラックスおよびそれを用いる溶融Ｚｎ－Ａｌ－Ｍｇ系めっき鋼成形品の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813044A (en) * 1954-03-29 1957-11-12 Poor & Co Galvanizing process and flux composition
US3030241A (en) * 1959-02-24 1962-04-17 Jr Frederick C Brightly Galvanizing flux composition and treatment
LU75821A1 (de) * 1976-09-17 1977-05-04
WO1987005337A1 (fr) * 1986-03-04 1987-09-11 S.A. Floridienne - Chimie N.V. Composition de flux sans fluorures pour la galvanisation a chaud dans des bains de zinc aluminies
EP0363784A1 (de) * 1988-10-12 1990-04-18 BASF Aktiengesellschaft Flussmittel für die Feuerverzinkung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816188A (en) * 1972-12-18 1974-06-11 Du Pont Low-fuming galvanizing fluxes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813044A (en) * 1954-03-29 1957-11-12 Poor & Co Galvanizing process and flux composition
US3030241A (en) * 1959-02-24 1962-04-17 Jr Frederick C Brightly Galvanizing flux composition and treatment
LU75821A1 (de) * 1976-09-17 1977-05-04
WO1987005337A1 (fr) * 1986-03-04 1987-09-11 S.A. Floridienne - Chimie N.V. Composition de flux sans fluorures pour la galvanisation a chaud dans des bains de zinc aluminies
EP0363784A1 (de) * 1988-10-12 1990-04-18 BASF Aktiengesellschaft Flussmittel für die Feuerverzinkung

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004607A1 (en) * 1993-08-05 1995-02-16 Ferro Technologies, Inc. Lead-free galvanizing technique
US7811389B2 (en) 2005-12-20 2010-10-12 Teck Metals Ltd. Flux and process for hot dip galvanization
EP2447389A4 (de) * 2009-06-25 2016-08-17 Nippon Steel & Sumitomo Metal Corp Hochfester zn-al-plattierter stahldraht für brücken mit ausgezeichneter korrosionsbeständigkeit und ermüdungserscheinungseigenschaften, und herstellungsverfahren dafür
US10745792B2 (en) 2012-10-25 2020-08-18 Fontaine Holdings Nv Continuous single-dip process for galvanization of steel long products into Zn—Al—Mg alloys
EP2725114A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Flussmittelzusammensetzungen zur Stahlverzinkung
EP2725115A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Flussmittelzusammensetzungen zur Stahlverzinkung
EP2725117A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Kontinuierliches Einzeldip-Verfahren zur Verzinkung von langen Stahlprodukten in Zn-Al-Mg-Legierungen
EP2725116A1 (de) 2012-10-25 2014-04-30 Fontaine Holdings NV Kontinuierliches Einzeldip-Verfahren zur Verzinkung von langen Stahlprodukten in Zn-Al-Mg-Legierungen
US10801096B2 (en) 2012-10-25 2020-10-13 Fontaine Holdings Nv Continuous single-dip process for galvanization of steel long products into Zn—Al—Mg alloys
US10793940B2 (en) 2012-10-25 2020-10-06 Fontaine Holdings Nv Flux compositions for steel galvanization
EP2915607A1 (de) 2014-03-04 2015-09-09 Fontaine Holdings NV Verzinkte Metallobjekte und deren Herstellungsverfahren
US10399137B2 (en) 2014-03-04 2019-09-03 Fontaine Holdings, Nv Galvanized metal objects and their manufacturing process
CN107525739A (zh) * 2017-08-22 2017-12-29 山东交通学院 一种测定液体融雪剂最低使用温度的试验装置及试验方法
CN107525739B (zh) * 2017-08-22 2023-08-29 山东交通学院 一种测定液体融雪剂最低使用温度的试验装置及试验方法

Also Published As

Publication number Publication date
KR100392565B1 (ko) 2003-10-22
DE69129180D1 (de) 1998-05-07
JPH079056B2 (ja) 1995-02-01
ES2116991T3 (es) 1998-08-01
JPH04202751A (ja) 1992-07-23
CA2056666A1 (en) 1993-06-03
CA2056666C (en) 1995-05-30
AU639843B2 (en) 1993-08-05
AU8828591A (en) 1992-06-04
EP0488423B1 (de) 1998-04-01
DE69129180T2 (de) 1998-11-12
KR920010014A (ko) 1992-06-26

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