EP0321478B1 - Poudre de coulee destinee a etre utilisee dans la production d'acier en lingots par coulee en source et procede d'utilisation - Google Patents
Poudre de coulee destinee a etre utilisee dans la production d'acier en lingots par coulee en source et procede d'utilisation Download PDFInfo
- Publication number
- EP0321478B1 EP0321478B1 EP87905525A EP87905525A EP0321478B1 EP 0321478 B1 EP0321478 B1 EP 0321478B1 EP 87905525 A EP87905525 A EP 87905525A EP 87905525 A EP87905525 A EP 87905525A EP 0321478 B1 EP0321478 B1 EP 0321478B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mold
- casting powder
- steel
- expandable graphite
- molten steel
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 62
- 239000010959 steel Substances 0.000 title claims abstract description 62
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000005266 casting Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 230000004907 flux Effects 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910002804 graphite Inorganic materials 0.000 claims description 31
- 239000010439 graphite Substances 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010405 reoxidation reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
- B22D27/06—Heating the top discard of ingots
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/12—Appurtenances, e.g. for sintering, for preventing splashing
Definitions
- This invention relates to mold powders employed in ingot steel production. More specifically, the present invention discloses a casting powder to be employed in bottom pour steel molds which has the unique ability to act as both a bottom pour flux and a hot topping compound.
- a sealed bag of bottom pour flux is suspended in the mold approximately six to eighteen inches above the inlet for the molten steel.
- the bottom pour flux consists of chemical compounds which melt and spread rapidly across the surface of the molten steel.
- the molten slag coating the surface of the steel acts to create the correct menisus shape and prevents oxidation of steel surface.
- the molten slag insulates the surface of the molten steel to slow solidification, and spreads a thin coat of homogenous glass between the mold and the molten steel to allow constant heat transfer and solidification and thus lessen thermally induced stresses and resultant cracking.
- the flux absorbs impurities such as deoxidation and reoxidation products and refractory particles.
- the bag containing the bottom pour flux burns upon the introduction of the molten steel into the mold thus automatically releasing the flux.
- hot topping compounds are not without its detractions. Adding hot topping compound is cumbersome, labor intensive, environmentally disruptive, and may contaminate the ingot steel.
- a method of ingot casting is known from US-A-3 934 637 including bottom pouring molten metal into an ingot mold to form an ingot wherein there is located in the ingot mold prior to the commencement of pouring, a bonded composition comprising one or more fluxing agents and expandable graphite.
- the bonded composition is borne up on the rising metal surface.
- the composition serves to protect the walls of the casting mold.
- Expandable graphite means particulate graphite the particles of which on heating, intumesce to give a low density highly heat insulative vermicular structure.
- the patent specification is silent on the exact rate of expansion of the graphite. It is only stated that the graphite is to expand to many times its original volume.
- the expandable graphite may be present in a range of 0.5 % to 10.0 % by weight.
- a heat-insulating antipiping composition is known from US-A-3 811 898. This molten metal is applied to the surface of the molten metal in the feeder head after the metal has been poured into the mold. The amount of antipiping composition applied is sufficient to give a layer of expanded heat insulative material on the top of the molten metal to prevent excessive piping during the solidification of the metal.
- the first mentioned patent discloses a composition serving to protect the walls of the casting mold
- the second mentioned patent discloses a composition serving to prevent excessive piping during solidification.
- the composition according to the second mentioned patent is applied only after the molten metal has been poured into the mold.
- This object is achieved by the invention by a method for increased efficiency of protecting a steelmaker's mold and a steel ingot as bottom poured into the mold, including protecting against excessive piping of the steel which tends to occur when the molten steel cools too rapidly in the mold, comprising introducing into the mold a predetermined quantity of a casting powder, comprising chemical components combined to produce a bottom pour flux, and including an expandable graphite, pouring molten steel into said mold and covered with said casting powder to cause a substantial portion of said casting powder to rise to the vicinity of the top of said mold, thinly coating the side walls of said mold as it rises, and expanding into a thick insulative blanket on top of the molten steel of a sufficient insulative quality to avoid need for a hot topping compound limiting the steel's rate of cooling and thereby minimizing the piping of the ingot, wherein an expandable graphite is used that expands to 100 - 300 times its volume and comprises 4.0 to 12.0 % by weight of the composition of said casting powder.
- the casting powder used in this method may be automatically dispensed, is economic to produce and use, entails little environmental risk, and does not contribute to ingot contamination.
- the casting powder provides the benefits of both the prior methods and products separately and individually serving to protect the walls of the casting mold and to prevent excessive piping during the solidification of the cast metal.
- the method according to the invention entails introducing a compound known as "expandable graphite" in place of a portion of the carbon component of a standard bottom pour flux.
- the resulting mixture provides all the insulative and protective benefits of standard bottom pour fluxes as well as the full insulative requirements of hot topping compounds.
- the casting powder used in the method according to the invention is cleanly and automatically dispersed upon introduction of molten steel into the steel ingot molds. It eliminates the noxious by-products of hot topping compound and its potentially contaminating effect of "core of debris", and does not require the labor input demanded for applicatikon of hot topping compound.
- the invention also relates to a casting powder for use in the aforementioned method.
- This powder comprises a mixture of chemical components to produce a bottom pour flux which coats and protects the top and sides of molten steel as it is introduced into the mold and including an expandable graphite component, which expands to form a thick insulative blanket on top of the molten steel of sufficient insulative quality to avoid need for a hot topping compound, limiting the steel's rate of cooling and thereby minimizing piping of the ingot, wherein the expandable graphite is of a type that expands 100 - 300 times its volume and comprises 4.0 to 12.0 % by weight of the composition of said mixture.
- the present invention is directed to casting powders for use in ingot steel production through bottom pour process. Instead of the bottom pour flux and the hot topping compound presently employed, the present invention substitutes a single casting powder which provides the benefits of both the prior products.
- the present invention entails introducing a compound known as "expandable graphite" in place of a portion of the carbon component of a standard bottom pour flux.
- the resulting mixture provides all the insulative and protective benefits of standard bottom pour fluxes as well as the full insulative requirements of hot topping compounds.
- the present invention is cleanly and automatically dispersed upon introduction of molten steel into the steel ingot molds. It eliminates the noxious by-products of hot topping compound and its potentially contaminating effect of "core of debris,” and does not require the labor input demanded for application of hot topping compound.
- the present invention provides a mixture of chemical components which function as a unique casting powder for bottom pour ingot steel production.
- the present invention combines the crucial properties of both bottom pour fluxes and hot topping compounds into a single, easily dispensed, composition.
- Bottom pour fluxes (or powders) presently employed are required to have specific qualities for covering and protecting molten steel rising in an ingot mold. These include: molten slag layer to completely coat the molten steel, to insulate, maintain a proper surface shape, protect against oxidation, and absorb deoxidation and reoxidation products; and an ability to form a thin layer of homogenous glass between the molten steel and the side walls of the mold so as to insulate, reduce thermally induced stresses and thus decrease cracking.
- a composition of a traditional bottom pour flux may comprise the following: Constituent Percentage (%) Range by Weight Silica (SiO2) 30.0 - 35.0% Aluminum Oxide (Al2O3) 15.0 - 17.0 Calcium Oxide (CaO) 6.5 - 8.0 Iron Oxide (Fe2O3) 4.0 - 6.0 Alkali Oxide 5.5 - 8.0 Carbon (C) 5.0 - 27.0
- Hot topping compounds have only one primary purpose: to provide a thick insulative blanket on top of the molten steel to reduce the heat loss from the top to avoid "pipe.” Pipe is a condition which occurs when there is no molten steel to feed the shrinkage cavity formed due to ingot solidification.
- Expandable graphite is produced through treatment of high grade natural crystalline graphite through oxidation or electrolysis by various oxidising materials. It is commercially available in a number of grades from graphite suppliers.
- expandable graphite When expandable graphite is heated rapidly it expands along the C-axis of the crystal to a magnitude of 40 to 300 times its original size.
- Expandable graphite has different expansion rates according to its quality. It is desired to use expandable graphite that expands between 100 and 300 times its volume within the percentage weight range provided above. It is believed that ideally an expansion of 200 to 250 times its volume at a percentage weight of 6.0 to 8.0% should be employed.
- the casting powder has a viscosity nearly identical to that of standard bottom pour flux (i.e. at 1500°C, bottom pour flux has a viscosity of approximately 50-200 poise, the present invention produces a flux with a viscosity of 50-200 poise). Moreover, under pressure the present invention produces a unique quality compressio product having anistrophy. This results in a substance perfectly suitable to properly coat between the molten steel and the side walls of the ingot mold during pouring. Thus, the casting powder produced provides superior results as both a bottom pour flux and a hot topping compound.
- the casting powder is dispersed in the same manner as standard bottom pour flux. It is placed in a combustible container or bag, such as paper bag with grommet reinforcements, and suspended six to eighteen inches above the bottom of the ingot mold. It can also be preformed into a board and placed at the bottom of the mold. The incoming molten steel consumes the container or dissolves the board causing the release of the powder. The powder then rapidly spreads across the surface of the incoming molten steel. This is a clean, automatic process which requires little human input and supervision.
- the benefits of the present invention are realized through the elimination of hot topping compound. Personnel are no longer required to be stationed above the molds to apply the insulative material. Atmospheric dust from the hot topping compound and "core of debris" are also eliminated. Additionally, no smoke products are produced whatsoever. Despite the somewhat higher cost of substituting expandable graphite for standard graphite, the elimination of hot topping compound and the considerable cost savings in application provide a considerable overall cost savings.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Continuous Casting (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
Claims (7)
- Procédé pour augmenter l'efficacité de protection d'une lingotière d'aciérie et d'un lingot d'acier à l'état de coulée par le fond dans la lingotière, incluant la protection contre une formation excessive de retassures dans l'acier, qui tend à se produire quand l'acier fondu refroidit trop rapidement dans la lingotière, comprenant :
l'introduction dans la lingotière d'une quantité prédéterminée d'une poudre de coulée, formée de composants chimiques combinés pour produire un fondant de coulée par le fond, et incluant un graphite expansible,
la coulée de l'acier fondu dans la lingotière et recouvert par cette poudre de coulée pour amener une partie substantielle de cette poudre de coulée à monter à proximité du sommet de la lingotière, recouvrant finement les parois latérales de la lingotière lors de la montée, et la l'expansion en une épaisse couche isolante au sommet de l'acier fondu d'une qualité suffisamment isolante pour éviter la nécessité d'un agent de masselotte chaude, limitant la vitesse de refroidissement de l'acier et minimisant ainsi la formation de retassures dans le lingot,
dans lequel il est fait usage d'un graphite expansible qui s'expanse de 100 à 300 fois son volume et forme 4,0 à 12,0% en poids de la composition de cette poudre de coulée. - Procédé suivant la revendication 1, caractérisé par l'utilisation d'un graphite expansible qui s'expanse de 200 à 250 fois son volume et forme 6,0 à 8,0% en poids de la composition de cette poudre de coulée.
- Procédé suivant la revendication 1, caractérisé en ce que la poudre de coulée est placée dans un récipient combustible suspendu à au moins 150 mm au-dessus du fond de la lingotière.
- Procédé suivant la revendication 3, caractérisé en ce que le récipient combustible est un sac combustible.
- Procédé suivant la revendication 1, caractérisé en ce que la poudre de coulée est façonnée en forme de plaque et placée au fond de la lingotière.
- Poudre de coulée utilisée dans le procédé suivant l'une quelconque des revendications précédentes, comprenant :
un mélange de composants chimiques pour produire un fondant de coulée par le fond qui recouvre et protège le sommet et les côtés de l'acier fondu quand il est introduit dans la lingotière, et incluant un graphite expansible, qui s'expanse pour former une épaisse couche isolante au sommet de l'acier fondu, d'une qualité suffisamment isolante pour éviter la nécessité d'un agent de masselotte chaude, limitant la vitesse de refroidissement de l'acier et minimisant ainsi la formation de retassures dans le lingot,
dans laquelle le graphite expansible est d'un type qui s'expanse de 100 à 300 fois son volume et forme 4,0 à 12,0% en poids de la composition de ce mélange. - Poudre de coulée suivant la revendication 6, caractérisée en ce que le graphite expansible est d'un type qui s'expanse de 200 à 300 fois son volume et forme 6,0 à 8,0% en poids de la composition de ce mélange.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87905525T ATE96708T1 (de) | 1986-08-13 | 1987-08-10 | Giesspulver bei der blockstahlerzeugung im unterguss und verfahren zu seiner verwendung. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US89606786A | 1986-08-13 | 1986-08-13 | |
US896067 | 1986-08-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0321478A1 EP0321478A1 (fr) | 1989-06-28 |
EP0321478A4 EP0321478A4 (fr) | 1990-04-10 |
EP0321478B1 true EP0321478B1 (fr) | 1993-11-03 |
Family
ID=25405572
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87905525A Expired - Lifetime EP0321478B1 (fr) | 1986-08-13 | 1987-08-10 | Poudre de coulee destinee a etre utilisee dans la production d'acier en lingots par coulee en source et procede d'utilisation |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0321478B1 (fr) |
JP (1) | JPH01501536A (fr) |
KR (1) | KR880701599A (fr) |
AU (1) | AU604503B2 (fr) |
BR (1) | BR8707766A (fr) |
CA (1) | CA1285461C (fr) |
DE (1) | DE3788067T2 (fr) |
MX (1) | MX169019B (fr) |
WO (1) | WO1988001210A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0875320B1 (fr) * | 1997-04-30 | 2004-01-21 | Stopinc Aktiengesellschaft | Fermeture à tiroir pour récipients contenant un métal en fusion |
JP5366896B2 (ja) * | 2010-07-07 | 2013-12-11 | 株式会社神戸製鋼所 | 下注ぎ造塊方法 |
JP5807910B2 (ja) * | 2011-11-15 | 2015-11-10 | 山陽特殊製鋼株式会社 | 下注ぎ造塊用の被覆剤 |
JP6609139B2 (ja) * | 2015-08-24 | 2019-11-20 | 山陽特殊製鋼株式会社 | 下注ぎ造塊法のための被覆剤 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3308514A (en) * | 1965-01-07 | 1967-03-14 | Dow Chemical Co | Method of hot topping using vermicular graphite |
GB1298701A (en) * | 1969-11-12 | 1972-12-06 | Foseco Int | Heat-insulating antipiping compounds |
GB1431787A (en) * | 1973-03-28 | 1976-04-14 | Foseco Int | Casting of molten metals |
JPS5253727A (en) * | 1975-10-28 | 1977-04-30 | Fuoseko Japan Rimitetsudo Yuug | Formed additive for mold |
JPS6038201B2 (ja) * | 1978-09-04 | 1985-08-30 | 石川島播磨重工業株式会社 | 圧延材端部形状制御装置 |
-
1987
- 1987-08-10 EP EP87905525A patent/EP0321478B1/fr not_active Expired - Lifetime
- 1987-08-10 WO PCT/US1987/001958 patent/WO1988001210A1/fr active IP Right Grant
- 1987-08-10 DE DE3788067T patent/DE3788067T2/de not_active Expired - Fee Related
- 1987-08-10 BR BR8707766A patent/BR8707766A/pt not_active Application Discontinuation
- 1987-08-10 JP JP62505033A patent/JPH01501536A/ja active Pending
- 1987-08-10 AU AU78567/87A patent/AU604503B2/en not_active Ceased
- 1987-08-12 CA CA000544344A patent/CA1285461C/fr not_active Expired - Fee Related
- 1987-08-18 MX MX007790A patent/MX169019B/es unknown
-
1988
- 1988-04-13 KR KR1019880700405A patent/KR880701599A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
AU7856787A (en) | 1988-03-08 |
KR880701599A (ko) | 1988-11-04 |
WO1988001210A1 (fr) | 1988-02-25 |
CA1285461C (fr) | 1991-07-02 |
DE3788067D1 (de) | 1993-12-09 |
EP0321478A1 (fr) | 1989-06-28 |
MX169019B (es) | 1993-06-17 |
EP0321478A4 (fr) | 1990-04-10 |
AU604503B2 (en) | 1990-12-20 |
BR8707766A (pt) | 1989-08-15 |
JPH01501536A (ja) | 1989-06-01 |
DE3788067T2 (de) | 1994-05-19 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19890310 |
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