EP0099840B1 - Electrolytic pot for the production of aluminium having a conductive floating screen - Google Patents
Electrolytic pot for the production of aluminium having a conductive floating screen Download PDFInfo
- Publication number
- EP0099840B1 EP0099840B1 EP83420109A EP83420109A EP0099840B1 EP 0099840 B1 EP0099840 B1 EP 0099840B1 EP 83420109 A EP83420109 A EP 83420109A EP 83420109 A EP83420109 A EP 83420109A EP 0099840 B1 EP0099840 B1 EP 0099840B1
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- EP
- European Patent Office
- Prior art keywords
- electrolytic tank
- tank according
- screen
- floating
- floating screen
- 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.)
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
Definitions
- the present invention relates to a tank for the production of aluminum by electrolysis of alumina dissolved in the molten cryolite according to the Hall-Héroult process, comprising a floating conductive screen, between the anode and the cathode.
- the electrical energy consumption is at least 13,000. KWh per tonne of metal, and often exceeds 14,000.
- the voltage drop in the electrolyte represents about 1.5 volts, so it is responsible for more than a third of the total energy consumption.
- cathodes based on electrically conductive refractories, such as titanium diboride TiB 2 , which is perfectly wet. by liquid aluminum and undergoes practically no attack by this metal at the temperature of electrolysis.
- Such cathodes have been described, in particular, in English patents 784,695, 784,696, 784,697 to BRITISH ALUMINUM C °, and in the article by KE BILLEHAUG and HA OYE in "ALUMINUM", Oct. 1980, pages 642. -648 and Nov. 1980, pages 713 to 718.
- the present invention constitutes another solution to the problem of reducing the interpolar distance without the risk of entraining the cathode aluminum towards the anode.
- FIGS. 1 and 2 represent different modes of implementing the invention:
- the floating conductive screen (1) consists of porous TiB 2 balls (2), but sealed on the surface, with an average density of 2.25.
- These balls can be manufactured, for example, according to the technique described in the French brevent 1,579,540 in the name of ALUMINUM PECHINEY, which consists in sintering a mixture of TiB 2 and a substance which can be removed at the sintering temperature.
- the diameter of these beads is between 5 and 50 mm and, preferably, between 10 and 40 mm.
- the lower diameter limit is related to manufacturing costs and the upper limit is approximately twice the planned interpolar distance.
- Such beads having a porosity of around 50% can be considered too fragile.
- the sealing can be carried out in two stages: deposition of a medium dense bonding layer to the plasma, then of a thin sealing layer by chemical deposition or else by a chemical vapor deposition carried out in two stages, the the first being performed at lower pressure and temperature than the second.
- the TiB 2 floating balls (2) form a substantially continuous layer at the interface (3) of the metal (4) and the electrolyte (5). It is this layer which forms the screen (1) between the anode (6) and the metal (4) and, at the same time, acts as cathode on which the liquid aluminum droplets produced by electrolysis are formed. These droplets wet the floating balls (2) and collect in the already formed layer (4). The risk of entrainment of the droplets towards the anode, where they would reoxidize, is therefore practically eliminated, which makes it possible to reduce the interpolar distance d to around 20 millimeters and to lower the voltage drop in the electrolyte to less than 1 volt.
- the floating balls (2) have been drawn above the interface (3), but it is obvious that their exact position depends on their density ratio with the bath and the metal.
- the floating screen is formed from beads based on TiB 2
- this shape is not compulsory and any other shape may be suitable, for example cylindrical elements which, according to their length / diameter ratio, will float with the axis in vertical or horizontal position.
- Flat discs for example, can be used.
- the largest dimension of the elements used does not exceed 50 mm and, preferably, 40 mm, that is to say twice the target interpolar distance.
- Figure 2 shows a solution in which the floating conductive screen is confined to the plumb of the anodes (6) by means of barriers (7) of dense refractory material. Openings (8) should preferably be made in these barriers to ensure the circulation of the liquid aluminum (4).
- the implementation of the invention allows a significant reduction in the interpolar distance, up to around 20 mm, without loss of the electrolysis yield.
- the potential difference at the terminals of the electrolysis cells thus modified is reduced from 4 volts to approximately 3.2 to 3.3 volts, with a proportional reduction in the energy consumption per tonne of aluminum produced.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Conductive Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Description
La présente invention concerne une cuve de production d'aluminium par électrolyse d'alumine dissoute dans la cryolithe fondue selon le procédé Hall-Héroult, comportant un écran conducteur flottant, entre l'anode et la cathode.The present invention relates to a tank for the production of aluminum by electrolysis of alumina dissolved in the molten cryolite according to the Hall-Héroult process, comprising a floating conductive screen, between the anode and the cathode.
Dans les installations les plus performantes produisant de l'aluminium selon le procédé Hall-Héroult la consommation d'énergie électrique est au moims égale à 13 000. KWh par tonne de métal, et dépasse souvent 14 000. Dans une cuve moderne fonctionnant sous une différence de potentiel de 4 volts, la chute de tension dans l'électrolyte représente environ 1,5 volts, elle est donc responsable de plus du tiers de la consommation énergétique totale. Elle est dûe à l'obligation de maintenir une distance suffisante entre l'anode et la nappe d'alumnium liquide cathodique (au moins égale à 40 mm et, le plus souvent, de l'ordre de 50 à 60 mm) pour éviter la réoxydation de l'aluminium entraîné vers l'anode par les mouvements de la nappe de métal liquide dûs aux effets magnétiques et facilités par la non-mouillabilité du substrat cathodique en carbone par l'aluminium liquide.In the most efficient installations producing aluminum according to the Hall-Héroult process, the electrical energy consumption is at least 13,000. KWh per tonne of metal, and often exceeds 14,000. In a modern tank operating under a potential difference of 4 volts, the voltage drop in the electrolyte represents about 1.5 volts, so it is responsible for more than a third of the total energy consumption. It is due to the obligation to maintain a sufficient distance between the anode and the cathode liquid alumnium sheet (at least equal to 40 mm and, more often than not, of the order of 50 to 60 mm) to avoid reoxidation of the aluminum entrained towards the anode by the movements of the sheet of liquid metal due to the magnetic effects and facilitated by the non-wettability of the cathode carbon substrate by liquid aluminum.
Pour réduire la distance interpolaire, sans provoquer l'entraînement de l'aluminium cathodique vers l'anode, on a proposé d'utiliser des cathodes à base de réfractaires électro- conducteurs, tels que le diborure de titane TiB2, qui est parfaitement mouillé par l'aluminium liquide et ne subit pratiquement pas d'attaque par ce métal à la température de l'électrolyse. De telles cathodes ont été décrites, en particulier, dans les brevets anglais 784 695, 784 696, 784 697 de BRITISH ALUMINIUM C°, et dans l'article de K.E. BILLEHAUG et H.A. OYE dans "ALUMINIUM", Oct. 1980, pages 642-648 et nov. 1980, pages 713 à 718.To reduce the interpolar distance, without causing the cathodic aluminum to drive towards the anode, it has been proposed to use cathodes based on electrically conductive refractories, such as titanium diboride TiB 2 , which is perfectly wet. by liquid aluminum and undergoes practically no attack by this metal at the temperature of electrolysis. Such cathodes have been described, in particular, in English patents 784,695, 784,696, 784,697 to BRITISH ALUMINUM C °, and in the article by KE BILLEHAUG and HA OYE in "ALUMINUM", Oct. 1980, pages 642. -648 and Nov. 1980, pages 713 to 718.
Un des problèmes majeurs que posent ces cathodes en diborure de titane est leur mise en solution progressive dans l'aluminum liquide, phénomène lent mais non négligeable, qui nécessite le remplacement périodique des éléments usés et implique l'arrêt total et le démontage de la cuve.One of the major problems posed by these titanium diboride cathodes is their gradual dissolution in liquid aluminum, a slow but not insignificant phenomenon, which requires the periodic replacement of worn elements and involves total stopping and dismantling of the tank. .
La présente invention constitue une autre solution au problème de la réduction de la distance interpolaire sans risque d'entraînement de l'aluminium cathodique vers l'anode.The present invention constitutes another solution to the problem of reducing the interpolar distance without the risk of entraining the cathode aluminum towards the anode.
Elle se caractérise par la mise en place, entre l'anode et la cathode à l'interface de la nappe d'aluminium liquide et du bain de cryolithe d'un écran flottant au niveau de ladite interface, constitué par le juxtaposition d'une pluralité d'éléments, conducteurs du courant électrique, formant une couche sensiblement continue, ces éléments étant étanchéisés en surface par un dépôt de diborure de titane d'une épaisseur au moins égale à 20 micromètres.It is characterized by the installation, between the anode and the cathode at the interface of the sheet of liquid aluminum and of the cryolite bath, of a floating screen at the level of said interface, constituted by the juxtaposition of a plurality of elements, conductors of electric current, forming a substantially continuous layer, these elements being sealed at the surface by a deposit of titanium diboride with a thickness at least equal to 20 micrometers.
Si l'on considère les densités respectives des éléments en présence à la température moyenne de l'électrolyse (≈960° C)
- Graphite: 1,7 - 1,9
- Electrolyte: 2,1 - 2,2
- Aluminium: 2,3
- TiB2: 4,5 - 4,6
il apparaît que l'écran flottant doit être constitué d'éléments dont la densité globale se situe entre environ 2,15 et 2,30 à 960°.If we consider the respective densities of the elements present at the average temperature of electrolysis (≈960 ° C)
- Graphite: 1.7 - 1.9
- Electrolyte: 2.1 - 2.2
- Aluminum: 2.3
- TiB 2 : 4.5 - 4.6
it appears that the floating screen must consist of elements whose overall density is between about 2.15 and 2.30 at 960 °.
Les figures 1 et 2 représentent différents modes de mise en oeuvre de l'invention:FIGS. 1 and 2 represent different modes of implementing the invention:
Sur la figure 1, l'écran conducteur flottant (1) est constitué par des billes (2) de TiB2 poreuses, mais étanchéisées en surface, d'une densité moyenne de 2,25. Ces billes peuvent être fabriquées par exemple selon la technique décrite dans le brevent français 1 579 540 au nom d'ALUMINIUM PECHINEY, et qui consiste à fritter un mélange de TiB2 et d'une substance éliminable à la température de frittage. Le diamètre de ces billes est compris entre 5 et 50 mm et, de préférence, entre 10 et 40 mm. La limite inférieure de diamètre est liée aux coûts de fabrication et la limite supérieure correspond à environ deux fois la distance interpolaire prévue.In FIG. 1, the floating conductive screen (1) consists of porous TiB 2 balls (2), but sealed on the surface, with an average density of 2.25. These balls can be manufactured, for example, according to the technique described in the French brevent 1,579,540 in the name of ALUMINUM PECHINEY, which consists in sintering a mixture of TiB 2 and a substance which can be removed at the sintering temperature. The diameter of these beads is between 5 and 50 mm and, preferably, between 10 and 40 mm. The lower diameter limit is related to manufacturing costs and the upper limit is approximately twice the planned interpolar distance.
De telles billes ayant une porosité d'environ 50 % peuvent être estimées trop fragiles. Dans ce cas, on fritte un mélange de TiB2 et de nitrure de bore (d = 2,20 à 2,25 à 960°) ou de graphit (d = 1,7 à 1,9), avec la proportion voulue de substance éliminable à chaud pour obtenir une densité finale sensiblement égale à 2,25 à 960° C.Such beads having a porosity of around 50% can be considered too fragile. In this case, a mixture of TiB 2 and boron nitride (d = 2.20 to 2.25 at 960 °) or graphit (d = 1.7 to 1.9) is sintered, with the desired proportion of hot eliminable substance to obtain a final density substantially equal to 2.25 at 960 ° C.
Il est indispensable d'étanchéiser les billes par un revêtement superficiel pour éviter leur imprégnation progressive par l'électrolyte et/ou le métal, qui détruirait leur flottabilité. Cette étanchéisation est effectuée par différents procédés connus permettant d'effectuer un dépôt comptact de TiB2, par exemple la projection au plasma ou le dépôt chimique. L'épaisseur de cette couche étanche est suffisante pour que la dissolution par l'aluminium liquide permette une durée de vie d'au moins quelques années, c'est-à-dire au moins égale à 20 micromètres.It is essential to seal the balls by a surface coating to avoid their progressive impregnation by the electrolyte and / or the metal, which would destroy their buoyancy. This sealing is carried out by various known methods making it possible to carry out a compact deposition of TiB 2 , for example plasma spraying or chemical deposition. The thickness of this tight layer is sufficient for the dissolution by liquid aluminum to allow a lifetime of at least a few years, that is to say at least equal to 20 micrometers.
L'étanchésation peut être effectuée en deux étapes: dépôt d'une couche d'accrochage moyennement dense au plasma, puis d'une couche fine d'étanchéité par dépôt chimique ou encore par un dépôt chimique en phase vapeur effectué en deux étepes, la première s'effectuant à pression et température plus basses que la seconde.The sealing can be carried out in two stages: deposition of a medium dense bonding layer to the plasma, then of a thin sealing layer by chemical deposition or else by a chemical vapor deposition carried out in two stages, the the first being performed at lower pressure and temperature than the second.
Une autre solution, pour obtenir la densité moyenne de 2,25 consiste à fabriquer des billes composites avec un noyau en graphite et une écorce en TiB2 compact, la proportion pondérale des deux constituants étant déterminée pour obtenir d = 2,25 (sensiblement 20 % de TiB2 et 80 % de graphite), la qualité de graphite étant alors choisie pour que le coefficient de dilation du graphite soit sensiblement égal à celui de TiB2 entre 0 et 1 000° C.Another solution, to obtain the average density of 2.25, consists in manufacturing composite balls with a graphite core and a compact TiB 2 shell, the proportion by weight of the two constituents being determined to obtain d = 2.25 (substantially 20 % of TiB 2 and 80% of graphite), the quality of graphite then being chosen so that the coefficient of expansion of the graphite is substantially equal to that of TiB 2 between 0 and 1000 ° C.
Les billes flottantes (2) en TiB2 forment une couche sensiblement continue à l'interface (3) du métal (4) et de l'électrolyte (5). C'est cette couche qui forme l'écran (1) entre l'anode (6) et le métal (4) et, en même temps, agit comme cathode sur laquelle se forment les gouttelettes d'aluminium liquide produites par l'électrolyse. Ces gouttelettes mouillent les billes flottantes (2) et se rassemblent dans la couche déjà formée (4). Le risque d'entraînement des gouttelettes vers l'anode, où elles se réoxyderaient, est donc pratiquement supprimé, ce qui permet de réduire la distance interpolaire d à environ 20 millimètres et d'abaisser la chute de tension dans l'électrolyte à moins de 1 volt. Sur les figures 1 et 2, les billes flottantes (2) ont été dessinées au-dessus de l'interface (3), mais il est bien évident que leur position exacte dépend de leur rapport de densité avec le bain et le métal.The TiB 2 floating balls (2) form a substantially continuous layer at the interface (3) of the metal (4) and the electrolyte (5). It is this layer which forms the screen (1) between the anode (6) and the metal (4) and, at the same time, acts as cathode on which the liquid aluminum droplets produced by electrolysis are formed. These droplets wet the floating balls (2) and collect in the already formed layer (4). The risk of entrainment of the droplets towards the anode, where they would reoxidize, is therefore practically eliminated, which makes it possible to reduce the interpolar distance d to around 20 millimeters and to lower the voltage drop in the electrolyte to less than 1 volt. In FIGS. 1 and 2, the floating balls (2) have been drawn above the interface (3), but it is obvious that their exact position depends on their density ratio with the bath and the metal.
Bien que l'invention ait été décrite dans le cas particulier eù l'ecran flottant est formé de billes à base de TiB2, cette forme n'est pas obligatoire et tout autre forme peut convenir, par exemple des éléments cylindriques qui, selon leur rapport longueur/diamètre, flotteront avec l'axe en position verticale ou horizontale. Des disques plats, par exemple, peuvent être utilisés. Dans un tel cas, (éléments non liés entre eux), il est souhaitable que la plus grande dimension des éléments utilisés ne dépasse par 50 mm et, de préférence, 40 mm c'est-à, dire deux fois la distance interpolaire visée.Although the invention has been described in the particular case in which the floating screen is formed from beads based on TiB 2 , this shape is not compulsory and any other shape may be suitable, for example cylindrical elements which, according to their length / diameter ratio, will float with the axis in vertical or horizontal position. Flat discs, for example, can be used. In such a case, (elements not linked to each other), it is desirable that the largest dimension of the elements used does not exceed 50 mm and, preferably, 40 mm, that is to say twice the target interpolar distance.
La solution de la figure 1 présente l'inconvénient que tout l'interface du métal (4) et de l'électrolyte (5) est recouverte par l'écran de billes (2) alors que sa présence n'est nécessaire qu'à l'aplomb des anodes (6).The solution of Figure 1 has the disadvantage that the entire interface of the metal (4) and the electrolyte (5) is covered by the screen of balls (2) while its presence is only necessary plumb with the anodes (6).
La figure 2 réprésente une solution dans laquelle l'écran conducteur flottant est confiné à l'aplomb des anodes (6) au moyen des barrières (7) en matériau réfractaire dense. Des ouvertures (8) doivent être, de préférence, ménagées dans ces barrières pour assurer la circulation de l'aluminium liquide (4).Figure 2 shows a solution in which the floating conductive screen is confined to the plumb of the anodes (6) by means of barriers (7) of dense refractory material. Openings (8) should preferably be made in these barriers to ensure the circulation of the liquid aluminum (4).
La mise en oeuvre de l'invention, sous les différentes variantes, permet une réduction importante de la distance interpolaire, jusqu'aux environs de 20 mm, sans perte du rendement d'électlolyse. La différence de potentiel aux bornes des cellules d'électrolyse ainsi modifiées est réduite de 4 volts à environ 3,2 à 3,3 volts, avec diminution proportionnelle de la consommation énergétique par tonne d'aluminium produite.The implementation of the invention, under the different variants, allows a significant reduction in the interpolar distance, up to around 20 mm, without loss of the electrolysis yield. The potential difference at the terminals of the electrolysis cells thus modified is reduced from 4 volts to approximately 3.2 to 3.3 volts, with a proportional reduction in the energy consumption per tonne of aluminum produced.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8211873 | 1982-06-30 | ||
| FR8211873A FR2529580B1 (en) | 1982-06-30 | 1982-06-30 | ELECTROLYSIS TANK FOR THE PRODUCTION OF ALUMINUM, COMPRISING A FLOATING CONDUCTIVE SCREEN |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0099840A1 EP0099840A1 (en) | 1984-02-01 |
| EP0099840B1 true EP0099840B1 (en) | 1986-08-13 |
Family
ID=9275740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83420109A Expired EP0099840B1 (en) | 1982-06-30 | 1983-06-29 | Electrolytic pot for the production of aluminium having a conductive floating screen |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4533452A (en) |
| EP (1) | EP0099840B1 (en) |
| JP (1) | JPS5920484A (en) |
| KR (1) | KR840006510A (en) |
| AU (1) | AU562447B2 (en) |
| BR (1) | BR8303459A (en) |
| CA (1) | CA1190892A (en) |
| DE (1) | DE3365289D1 (en) |
| ES (1) | ES8403984A1 (en) |
| FR (1) | FR2529580B1 (en) |
| GR (1) | GR77515B (en) |
| IN (1) | IN159794B (en) |
| NO (1) | NO832365L (en) |
| OA (1) | OA07473A (en) |
| SU (1) | SU1356967A3 (en) |
| YU (1) | YU140683A (en) |
| ZA (1) | ZA834761B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1244794A (en) * | 1983-11-29 | 1988-11-15 | Thomas J. Hudson | Aluminium reduction cells |
| US4631121A (en) * | 1986-02-06 | 1986-12-23 | Reynolds Metals Company | Alumina reduction cell |
| US4919782A (en) * | 1989-02-21 | 1990-04-24 | Reynolds Metals Company | Alumina reduction cell |
| US5129998A (en) * | 1991-05-20 | 1992-07-14 | Reynolds Metals Company | Refractory hard metal shapes for aluminum production |
| DE69316086T2 (en) * | 1992-05-25 | 1998-05-20 | Canon Kk | Magnetic developer and method for recognizing characters from magnetic ink |
| US5486278A (en) * | 1993-06-02 | 1996-01-23 | Moltech Invent S.A. | Treating prebaked carbon components for aluminum production, the treated components thereof, and the components use in an electrolytic cell |
| US5472578A (en) * | 1994-09-16 | 1995-12-05 | Moltech Invent S.A. | Aluminium production cell and assembly |
| US5753382A (en) * | 1996-01-10 | 1998-05-19 | Moltech Invent S.A. | Carbon bodies resistant to deterioration by oxidizing gases |
| WO2018092103A1 (en) * | 2016-11-19 | 2018-05-24 | Jan Petrus Human | Electrodes for use in the electro-extraction of metals |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE433408A (en) * | 1938-04-08 | |||
| US3287247A (en) * | 1962-07-24 | 1966-11-22 | Reynolds Metals Co | Electrolytic cell for the production of aluminum |
| GB1169012A (en) * | 1965-10-21 | 1969-10-29 | Montedison Spa | Furnace and Process for Producing, in Fused Bath, Metals from their Oxides, and Electrolytic Furnaces having Multiple Cells formed by Horizontal Bipolar Carbon Electrodes |
| US4338177A (en) * | 1978-09-22 | 1982-07-06 | Metallurgical, Inc. | Electrolytic cell for the production of aluminum |
| US4177128A (en) * | 1978-12-20 | 1979-12-04 | Ppg Industries, Inc. | Cathode element for use in aluminum reduction cell |
| US4224128A (en) * | 1979-08-17 | 1980-09-23 | Ppg Industries, Inc. | Cathode assembly for electrolytic aluminum reduction cell |
| GB2069530B (en) * | 1980-01-28 | 1984-05-16 | Diamond Shamrock Corp | Packed cathode bed for electrowinning metals from fused salts |
| CH644406A5 (en) * | 1980-04-03 | 1984-07-31 | Alusuisse | MELT FLOW ELECTROLYSIS CELL FOR THE PRODUCTION OF ALUMINUM. |
| US4349427A (en) * | 1980-06-23 | 1982-09-14 | Kaiser Aluminum & Chemical Corporation | Aluminum reduction cell electrode |
| ZA824255B (en) * | 1981-06-25 | 1983-05-25 | Alcan Int Ltd | Electrolytic reduction cells |
| CH648870A5 (en) * | 1981-10-23 | 1985-04-15 | Alusuisse | CATHOD FOR A MELTFLOW ELECTROLYSIS CELL FOR PRODUCING ALUMINUM. |
| FR2518124A1 (en) * | 1981-12-11 | 1983-06-17 | Pechiney Aluminium | FLOATING CATHODIC ELEMENTS BASED ON ELECTROCONDUCTIVE REFRACTORY FOR THE PRODUCTION OF ALUMINUM BY ELECTROLYSIS |
| US4436598A (en) * | 1983-09-28 | 1984-03-13 | Reynolds Metals Company | Alumina reduction cell |
-
1982
- 1982-06-30 FR FR8211873A patent/FR2529580B1/en not_active Expired
-
1983
- 1983-06-23 GR GR71761A patent/GR77515B/el unknown
- 1983-06-27 SU SU833610550A patent/SU1356967A3/en active
- 1983-06-28 OA OA58040A patent/OA07473A/en unknown
- 1983-06-28 BR BR8303459A patent/BR8303459A/en unknown
- 1983-06-28 CA CA000431303A patent/CA1190892A/en not_active Expired
- 1983-06-28 YU YU01406/83A patent/YU140683A/en unknown
- 1983-06-29 EP EP83420109A patent/EP0099840B1/en not_active Expired
- 1983-06-29 JP JP58118052A patent/JPS5920484A/en active Granted
- 1983-06-29 NO NO832365A patent/NO832365L/en unknown
- 1983-06-29 DE DE8383420109T patent/DE3365289D1/en not_active Expired
- 1983-06-29 ES ES523678A patent/ES8403984A1/en not_active Expired
- 1983-06-29 ZA ZA834761A patent/ZA834761B/en unknown
- 1983-06-30 KR KR1019830002971A patent/KR840006510A/en not_active Application Discontinuation
- 1983-06-30 AU AU16460/83A patent/AU562447B2/en not_active Ceased
- 1983-06-30 US US06/509,585 patent/US4533452A/en not_active Expired - Fee Related
- 1983-07-11 IN IN855/CAL/83A patent/IN159794B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2529580B1 (en) | 1986-03-21 |
| AU562447B2 (en) | 1987-06-11 |
| GR77515B (en) | 1984-09-24 |
| NO832365L (en) | 1984-01-02 |
| US4533452A (en) | 1985-08-06 |
| ZA834761B (en) | 1984-03-28 |
| SU1356967A3 (en) | 1987-11-30 |
| ES523678A0 (en) | 1984-04-01 |
| JPS5920484A (en) | 1984-02-02 |
| BR8303459A (en) | 1984-02-07 |
| OA07473A (en) | 1984-12-31 |
| CA1190892A (en) | 1985-07-23 |
| EP0099840A1 (en) | 1984-02-01 |
| DE3365289D1 (en) | 1986-09-18 |
| AU1646083A (en) | 1984-01-05 |
| IN159794B (en) | 1987-06-06 |
| ES8403984A1 (en) | 1984-04-01 |
| KR840006510A (en) | 1984-11-30 |
| JPS6141997B2 (en) | 1986-09-18 |
| YU140683A (en) | 1985-12-31 |
| FR2529580A1 (en) | 1984-01-06 |
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