EP0422192A1 - Process for coating a metallurgical container with a purifying layer and composition relating thereto, and protective coating thus obtained. - Google Patents

Process for coating a metallurgical container with a purifying layer and composition relating thereto, and protective coating thus obtained.

Info

Publication number
EP0422192A1
EP0422192A1 EP90907138A EP90907138A EP0422192A1 EP 0422192 A1 EP0422192 A1 EP 0422192A1 EP 90907138 A EP90907138 A EP 90907138A EP 90907138 A EP90907138 A EP 90907138A EP 0422192 A1 EP0422192 A1 EP 0422192A1
Authority
EP
European Patent Office
Prior art keywords
coating
composition
composition according
alkaline earth
refractory material
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
EP90907138A
Other languages
German (de)
French (fr)
Other versions
EP0422192B1 (en
Inventor
Jean-Charles Daussan
Gerard Daussan
Andre Daussan
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.)
Daussan SAS
Original Assignee
Daussan SAS
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Filing date
Publication date
Application filed by Daussan SAS filed Critical Daussan SAS
Priority to AT90907138T priority Critical patent/ATE99199T1/en
Publication of EP0422192A1 publication Critical patent/EP0422192A1/en
Application granted granted Critical
Publication of EP0422192B1 publication Critical patent/EP0422192B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/02—Linings

Definitions

  • the present invention relates to a method for coating a metallurgical container, such as a tundish or ladle, with a purifying coating.
  • purifying coating is meant a coating capable of reducing pollution of the liquid metal by impurities such as oxides.
  • means are currently used such as pouring tubes interposed between the ladle and the tundish and covering powders. arranged on the surface of the liquid metal.
  • Coatings are known for metallurgical vessels, in particular flow distributors, obtained by spraying a composition in the form of an aqueous slurry containing refractory particles, such as SiO 2, Al 2 O 3, gO or a mixture thereof, and a binder. organic or inorganic. These particles sinter under the effect of the heat of the liquid metal poured into the container, which ensures the cohesion of the coating.
  • refractory particles such as SiO 2, Al 2 O 3, gO or a mixture thereof
  • a binder organic or inorganic.
  • Coatings obtained by applying raw dolomite or calcium carbonate are also known.
  • Such coatings have purifying properties with respect to liquid metal. These properties are mainly based on the greed of CaO for oxides which pollute the metal such as AI2O3, FeO, ⁇ 2O3, giving compounds which are more fusible than the constituents and which migrate towards the slag.
  • aqueous mixture comprising approximately 98% of raw dolomite and 2% of sodium silicate as a binder.
  • the coating was fully baked to around 900 ° C, in order to release the CO2 from the dolomite.
  • the coating thus cooked had a porous structure whose mechanical strength was insufficient to resist the abrasion caused by the liquid metal.
  • REPLACEMENT SHEET forming a mold so that this procedure is of no industrial interest.
  • the Applicant has continued its research in order to discover an industrially acceptable solution making it possible to produce a purifying coating from raw dolomite or calcite.
  • the object of the present invention is precisely to provide a method and a composition for producing such a purifying coating, and a coating obtained by the implementation of this method.
  • the invention thus relates to a method and a composition for coating the interior wall of a metallurgical container, so as to produce a purifying coating based on at least one oxide of an alkaline earth metal.
  • this process is characterized by the following stages:
  • composition is applied to the inner wall of the container containing at least one simple or multiple carbonate of alkaline earth metal added with a certain proportion of refractory material in grains, and
  • This composition is heated to remove the CO2 and possibly the water of constitution and / or hydration and obtain a layer of the alkaline earth metal oxide (s) of porous structure, the proportion of refractory material being sufficient to impart to the coating sufficient resistance to erosion of the liquid metal poured into the container.
  • the composition may also contain a certain proportion of either alkaline earth hydroxides or alkaline earth oxides capable of hydrating during wetting of the composition and of activating lime or magnesia sufficiently "in situ" during the preheating of said composition, ro days in order to impart sufficient resistance to the coating.
  • the method according to the invention thus makes it possible to obtain an economical purifying coating since it uses as starting material one or more alkaline earth carbonates such as dolomite or calcite.
  • the coating obtained has good resistance to erosion caused by the metal poured into the metallurgical vessel.
  • the coating according to the invention has a double function, namely the purifying function and the function of wear coating, so that it can advantageously replace all the wear and protective coatings applied so far which do not have no purifying function.
  • the merit of the present invention lies in the fact that it has surprisingly discovered that the addition of a certain proportion of refractory material to one or more simple or multiple alkaline earth carbonates made it possible to obtain, after baking, that is to say after the elimination of the CO 2, a structure having an erosion resistance markedly greater than that obtained in the absence of this refractory material.
  • the coating obtained in addition to its purifying properties due to the alkaline earth oxide which is obtained after baking, has a structure which is sufficiently porous to give it thermal insulation properties making it possible to limit the cooling of the liquid metal contained in the pouring container. Furthermore, the coating obtained according to the process according to the invention does not adhere strongly to the permanent refractory coating on which it is applied so that at the end of casting, it can be easily detached in order to 'coii ⁇ uer a new coating.
  • the aforementioned composition can be advantageously sprayed in the form of aqueous mud, with. About 15 to 20% by weight of water.
  • the composition can also be poured between the interior surface of the metallurgical container and a mold wall.
  • the coating is heated to the core around 900 ° C, to release the CO2 from the alkaline earth carbonate and optionally the water of constitution and / or hydration.
  • This heating can be carried out by any means such as a burner, electric heating elements by Joule effect or with emission of infrared radiation.
  • the single or multiple alkaline earth carbonate used in the composition is preferably a carbonate chosen from the following compounds: raw dolomite, raw calcite and their mixtures, dolomite being however preferred because of its low cost in the raw state (not calcined).
  • the composition used preferably contains a binder chosen from mineral binders such as for example: silicate or alkaline phosphate, organic such as for example phenolic resin, hydraulic such as, for example, cements, and mixtures thereof.
  • the refractory material added to the alkaline earth carbonate is preferably chosen from the following compounds:
  • REPLACEMENT SHEET The optimal proportions will depend on the desired effect. The higher the proportion of alkaline earth carbonate, the greater the purifying effect. Conversely, the higher the proportion of refractory material, the greater the resistance to erosion of the coating.
  • the proportion of refractory material is just sufficient to give the coating the desired resistance to erosion so as to preserve the purifying properties due to the alkaline earth oxide remaining after release of the CO2.
  • the elements containing calcium will be favored in the composition.
  • the presence of the binder is not compulsory, because a setting effect with water already exists in its absence.
  • the alkaline earth carbonate can be pure calcium carbonate or combined with another carbonate, for example magnesium carbonate, in the form of dolomite.
  • alkaline earth oxides cited as examples of refractory material can be replaced in whole or in part by hydroxides and / or sulphates, the latter being transformed into oxides during cooking.
  • the grains of the refractory material have at least partly a dimension greater than that of the grains of carbonates and / or hydroxides and / or alkaline earth sulfates.
  • REPLACEMENT SHEET In fact, the grains of carbonates, hydroxides and sulfates decompose the more easily and quickly the smaller they are.
  • the particle size can be adjusted as a function of the desired result, namely the porosity which gives insulating and / or sintering properties which ensures cohesion and resistance to erosion.
  • composition according to the invention also preferably contains up to 20% by weight of organic and / or mineral fibers.
  • composition according to the invention may also contain a carbonaceous matter in grains.
  • the composition additionally contains up to 5% by weight of a surfactant.
  • the aforementioned composition can be applied to the bottom and the lateral faces of a tundish, by spraying or molding in one or more layers a few centimeters thick.
  • one or more fluxes such as, for example: olivine, colemanite, borocalcite (calcium borate), iron oxide, fluoride, boric acid and its salts (borax) and their mixtures.
  • Dolomite and / or calcite and / or hydroxides and / or sulfates 30 to 95%, grain diameter ⁇ 3 mm, preferably ⁇ 1 mm
  • Refractory material 70 to 5%, grain diameter ⁇ 5 mm, preferably ⁇ 2 mm
  • Binder 0 to 15% Carbon: 0 to 5%
  • the composition and the particle size of the grains can vary from one layer to another depending on the desired properties.
  • REPLACEMENT PLEASE will contain more refractory material, and will contain fine particles to promote sintering.
  • the outer layer adjacent to the permanent refractory lining may be sinter less than the inner layer, so that it can be easily detached from the permanent lining at the end of casting.
  • the basicity of the inner layer may be favored by a high calcium content in order to obtain optimal purifying properties.
  • a coating in several layers to protect the interior wall of a metallurgical container can thus comprise: - an interior purifying layer of wear coming into contact with liquid steel, based on oxide of an alkaline earth metal (dolomite , hydroxides, sulfates, calcite, carbonates),
  • this layer may be either a sinterable layer at the temperatures involved, based on stable refractory oxide grains (for example based on magnesia and / or silica and / or alumina and / or zircon and / or zirconia), or alternatively an outer layer with little or very little sinterability of security based on stable refractory oxides added with carbon (less than 35% carbon).
  • This last layer can also play the role of a third layer with little or very little sinterability placed between the aforementioned safety layer and the permanent coating to avoid any clinging of the permanent coating, like any other partially, little or very little sinterable layer.
  • first purifying inner layer a second layer with little or very little sinterability or not sinterability, and a third outer sintering layer or at least partially sinterable.

Abstract

On applique sur la paroi intérieure d'un récipient métallurgique une composition renfermant un carbonate d'un métal alcalino-terreux additionné d'une certaine proportion de matière réfractaire en grains et on chauffe ce revêtement pour éliminer le CO2 et obtenir une couche d'oxyde dudit métal alcalino-terreux de structure poreuse. La proportion de matière réfractaire est suffisante pour conférer au revêtement une résistance suffisante à l'érosion du métal liquide coulé dans le récipient. Utilisation pour obtenir un revêtement épurant et ayant une bonne résistance à l'érosion.A composition containing a carbonate of an alkaline earth metal added with a certain proportion of refractory material in grains is applied to the inner wall of a metallurgical vessel and this coating is heated to remove the CO2 and obtain an oxide layer. of said alkaline earth metal of porous structure. The proportion of refractory material is sufficient to give the coating sufficient resistance to erosion of the liquid metal poured into the container. Use to obtain a purifying coating with good resistance to erosion.

Description

"Procédé pour revêtir un récipient métallurgique par un revêtement épurant et composition s'y rapportant, et revêtement de protection ainsi obtenu" "Method for coating a metallurgical vessel with a purifying coating and composition relating thereto, and protective coating thus obtained"
La présente invention concerne un procédé pour revêtir un récipient métallurgique, tel que répartiteur de coulée ou poche de coulée, par un revêtement épurant.The present invention relates to a method for coating a metallurgical container, such as a tundish or ladle, with a purifying coating.
Par revêtement épurant on entend un revêtement capable de réduire la pollution du métal liquide par des impuretés telles que des oxydes.By purifying coating is meant a coating capable of reducing pollution of the liquid metal by impurities such as oxides.
Pour limiter l'oxydation du métal liquide, on a actuellement recours à des moyens tels que des tubes de coulée intercalés entre la poche de coulée et le répartiteur de coulée et des poudres de couverture. disposées à la surface du métal liquide.To limit the oxidation of the liquid metal, means are currently used such as pouring tubes interposed between the ladle and the tundish and covering powders. arranged on the surface of the liquid metal.
Ces moyens ne permettent toutefois pas de réduire complètement la pollution du bain de métal.However, these means do not make it possible to completely reduce the pollution of the metal bath.
On connaît des revêtements pour récipients métallurgiques, en particulier de répartiteurs de coulée, obtenus par projection d'une composition sous forme de boue aqueuse renfermant des particules réfractaires, telles que Siθ2 , AI2O3 , gO ou un mélange de celles-ci, et un liant organique ou inorganique. Ces particules frittent sous l'effet de la chaleur du métal liquide coulé dans le récipient, ce qui assure la cohésion du revêtement. Toutefois, de tels revêtements ne possèdent pas de fonction épurante à l'égard du métal liquide, certains étant même polluants.Coatings are known for metallurgical vessels, in particular flow distributors, obtained by spraying a composition in the form of an aqueous slurry containing refractory particles, such as SiO 2, Al 2 O 3, gO or a mixture thereof, and a binder. organic or inorganic. These particles sinter under the effect of the heat of the liquid metal poured into the container, which ensures the cohesion of the coating. However, such coatings do not have a purifying function with respect to the liquid metal, some being even polluting.
On connaît par ailleurs, un revêtement obtenu par application de dolomie cuite, c'est-à-dire essentiellement de CaO et de MgO sous forme de grains mélangés avec un liant tel que par exemple une résine t ermodurcissable.There is also known a coating obtained by application of cooked dolomite, that is to say essentially of CaO and MgO in the form of grains mixed with a binder such as for example a termosetting resin.
On connaît également des revêtements obtenus par application de dolomie crue ou de carbonate de calcium.Coatings obtained by applying raw dolomite or calcium carbonate are also known.
LACEMENT Après application de ces revêtements, ceux-ci subissent un chauffage qui décompose le carbonate et/ou le liant. Il reste ainsi une couche poreuse constituée essentiellement de CaO et/ou de MgO ayant une densité inférieure à 1.LACING After applying these coatings, they undergo heating which decomposes the carbonate and / or the binder. There thus remains a porous layer essentially consisting of CaO and / or MgO having a density of less than 1.
De tels revêtements possèdent des propriétés épurantes vis-à-vis du métal liquide. Ces propriétés sont principalement basées sur l'avidité de CaO pour des oxydes qui polluent le métal tels que AI2O3 , FeO, β2O3 , en donnant des composés qui sont plus fusibles que les constituants et qui migrent vers la scorie.Such coatings have purifying properties with respect to liquid metal. These properties are mainly based on the greed of CaO for oxides which pollute the metal such as AI2O3, FeO, β2O3, giving compounds which are more fusible than the constituents and which migrate towards the slag.
Toutefois ces revêtements présentent l'inconvénient d'avoir une très faible résistance mécaniquet de sorte qu'ils ne résistent pas à l'abrasion causée par le métal liquide.However, these coatings have the drawback of having a very low mechanical resistance t so that they do not resist the abrasion caused by the liquid metal.
Pour remédier à ces inconvénients, la demanderesse a réalisé les deux essais suivants :To remedy these drawbacks, the applicant has carried out the following two tests:
Dans un premier essai, la demanderesse a appliqué dans un répartiteur de coulée un mélange aqueux comprenant environ 98% de dolomie crue et 2% de silicate de sodium en tant que liant.In a first test, the applicant applied in an pouring distributor an aqueous mixture comprising approximately 98% of raw dolomite and 2% of sodium silicate as a binder.
Après projection, le revêtement a été cuit à coeur jusqu'à environ 900°C, de façon à libérer le CO2 de la dolomie. Le revêtement ainsi cuit présentait une structure poreuse dont la résistance mécanique était insuffisante pour résister à l'abrasion engendrée par le métal liquide.After spraying, the coating was fully baked to around 900 ° C, in order to release the CO2 from the dolomite. The coating thus cooked had a porous structure whose mechanical strength was insufficient to resist the abrasion caused by the liquid metal.
Dans un second essai, la demanderesse a coulé le mélange précité dans l'espace compris entre la paroi intérieure du répartiteur de coulée et une paroi formant moule.In a second test, the applicant poured the above mixture into the space between the inner wall of the tundish and a wall forming a mold.
Après séchage à 130°C, il a été constaté que le revêtement ne présentait aucune résistance mécanique interne et se détruisait lors du retrait de la paroiAfter drying at 130 ° C, it was found that the coating had no internal mechanical resistance and was destroyed when the wall was removed
FEUILLE DE REMPLACEMENT formant moule de sorte que ce mode opératoire ne présente aucun intérêt industriel.REPLACEMENT SHEET forming a mold so that this procedure is of no industrial interest.
La demanderesse a poursuivi ses recherches afin de découvrir une solution industriellement acceptable permettant de réaliser un revêtement épurant à partir de dolomie crue ou de calcite.The Applicant has continued its research in order to discover an industrially acceptable solution making it possible to produce a purifying coating from raw dolomite or calcite.
Le but de la présente invention est précisément de proposer un procédé et une composition pour la réalisation d'un tel revêtement épurant, et un revêtement obtenu par la mise en oeuvre de ce procédé.The object of the present invention is precisely to provide a method and a composition for producing such a purifying coating, and a coating obtained by the implementation of this method.
L'invention vise ainsi un procédé et une composition pour revêtir la paroi intérieure d'un récipient métallurgique, de manière à réaliser un revêtement épurant à base d'au moins un oxyde d'un métal alcalino-terreux.The invention thus relates to a method and a composition for coating the interior wall of a metallurgical container, so as to produce a purifying coating based on at least one oxide of an alkaline earth metal.
Suivant l'invention, ce procédé est caractérisé par les étapes suivantes :According to the invention, this process is characterized by the following stages:
- on applique sur la paroi intérieure du récipient une composition renfermant au moins un carbonate simple ou multiple de métal alcalino-terreux additionné d'une certaine proportion de matière réfractaire en grains , eta composition is applied to the inner wall of the container containing at least one simple or multiple carbonate of alkaline earth metal added with a certain proportion of refractory material in grains, and
- on chauffe cette composition pour éliminer le CO2 et éventuellement l'eau de constitution et/ou d'hydratation et obtenir une couche du ou des oxydes de métal alcalino-terreux de structure poreuse, la proportion de matière réfractaire étant suffisante pour conférer au revêtement une résistance suffisante à l'érosion du métal liquide coulé dans le récipient. La composition peut contenir en outre, une certaine proportion soit d'hydroxydes alcalino-terreux, soit d'oxydes alcalino-terreux susceptibles de s'hydrater lors du mouillage de la composition et d'activer suffisamment "in situ" la chaux ou la magnésie lors du préchauffage de ladite composition, ro jours dans le but de conférer une résistance suffisante au revêtement. Le procédé selon l'invention permet ainsi d'obtenir un revêtement épurant économique puisqu'il utilise comme produit de départ un ou des carbonates alcalino-terreux tel que de la dolomie ou de la calcite. De plus, le revêtement obtenu présente une bonne résistance à 1 ' érosion provoquée par le métal coulé dans le récipient métallurgique.- This composition is heated to remove the CO2 and possibly the water of constitution and / or hydration and obtain a layer of the alkaline earth metal oxide (s) of porous structure, the proportion of refractory material being sufficient to impart to the coating sufficient resistance to erosion of the liquid metal poured into the container. The composition may also contain a certain proportion of either alkaline earth hydroxides or alkaline earth oxides capable of hydrating during wetting of the composition and of activating lime or magnesia sufficiently "in situ" during the preheating of said composition, ro days in order to impart sufficient resistance to the coating. The method according to the invention thus makes it possible to obtain an economical purifying coating since it uses as starting material one or more alkaline earth carbonates such as dolomite or calcite. In addition, the coating obtained has good resistance to erosion caused by the metal poured into the metallurgical vessel.
Ainsi, le revêtement selon l'invention présente une double fonction à savoir la fonction épurante et la fonction de revêtement d'usure, de sorte qu'il peut avantageusement remplacer tous les revêtements d'usure et de protection appliqués jusqu'à présent qui ne présentent pas de fonction épurante.Thus, the coating according to the invention has a double function, namely the purifying function and the function of wear coating, so that it can advantageously replace all the wear and protective coatings applied so far which do not have no purifying function.
Le mérite de la présente invention réside dans le fait d'avoir découvert de façon surprenante que l'addition d'une certaine proportion de matière réfractaire à un ou plusieurs carbonates alcalino-terreux simples ou multiples permettait d'obtenir après cuisson, c'est-à-dire après l'élimination du CO2 , une structure présentant une résistance à l'érosion nettement supérieure à celle obtenue en l'absence de cette matière réfractaire.The merit of the present invention lies in the fact that it has surprisingly discovered that the addition of a certain proportion of refractory material to one or more simple or multiple alkaline earth carbonates made it possible to obtain, after baking, that is to say after the elimination of the CO 2, a structure having an erosion resistance markedly greater than that obtained in the absence of this refractory material.
De plus, le revêtement obtenu, outre ses propriétés épurantes dues à l'oxyde alcalino-terreux qui est obtenu après la cuisson, présente une structure suffisamment poreuse pour lui conférer des propriétés d'isolation thermique permettant de limiter le refroidissement du métal liquide contenu dans le récipient de coulée. Par ailleurs, le revêtement obtenu selon le procédé conforme à l'invention n'adhère pas fortement au revêtement réfractaire permanent sur lequel il est appliqué e sorte qu'en fin de coulée, il peut être facilement détaché en vue ' coiiσuer un revêtement neuf. La composition précitée peut être avantageusement projetée sous forme de boue aqueuse, avec. 15 à 20% environ en poids d'eau.In addition, the coating obtained, in addition to its purifying properties due to the alkaline earth oxide which is obtained after baking, has a structure which is sufficiently porous to give it thermal insulation properties making it possible to limit the cooling of the liquid metal contained in the pouring container. Furthermore, the coating obtained according to the process according to the invention does not adhere strongly to the permanent refractory coating on which it is applied so that at the end of casting, it can be easily detached in order to 'coiiσuer a new coating. The aforementioned composition can be advantageously sprayed in the form of aqueous mud, with. About 15 to 20% by weight of water.
La composition peut également être coulée entre la surface intérieure du récipient métallurgique et une paroi formant moule.The composition can also be poured between the interior surface of the metallurgical container and a mold wall.
Après application, le revêtement est chauffé à coeur aux environs de 900°C, pour libérer le CO2 du carbonate alcalino-terreux et éventuellement l'eau de constitution et/ou d'hydratation. Ce chauffage peut être réalisé par tout moyen tel que brûleur, éléments chauffants électriques par effet Joule ou à émission de rayonnement infra-rouge.After application, the coating is heated to the core around 900 ° C, to release the CO2 from the alkaline earth carbonate and optionally the water of constitution and / or hydration. This heating can be carried out by any means such as a burner, electric heating elements by Joule effect or with emission of infrared radiation.
Le carbonate alcalino-terreux simple ou multiple utilisé dans la composition est de préférence un carbonate choisi parmi les composés suivants : dolomie crue, calcite crue et leurs mélanges, la dolomie étant cependant préférée en raison de son faible coût à l'état cru (non calciné) . Pour faciliter son application la composition utilisée renferme de préférence un liant choisi parmi les liants minéraux tels que par exemple : silicate ou phosphate alcalin, organiques tels que par exemple résine phénolique, hydrauliques tels que, par exemple, ciments, et leurs mélanges.The single or multiple alkaline earth carbonate used in the composition is preferably a carbonate chosen from the following compounds: raw dolomite, raw calcite and their mixtures, dolomite being however preferred because of its low cost in the raw state (not calcined). To facilitate its application, the composition used preferably contains a binder chosen from mineral binders such as for example: silicate or alkaline phosphate, organic such as for example phenolic resin, hydraulic such as, for example, cements, and mixtures thereof.
La matière réfractaire ajoutée au carbonate alcalino-terreux est de préférence choisie parmi les composés suivants :The refractory material added to the alkaline earth carbonate is preferably chosen from the following compounds:
- dolomie calcinée, chaux, magnésie, chrome magnésie, oxyde de chrome, silicate de zirconium, silice, silico-alumineux et/ou leurs mélanges.- calcined dolomite, lime, magnesia, chromium magnesia, chromium oxide, zirconium silicate, silica, silico-aluminous and / or mixtures thereof.
La composition pondérale des constituants principaux est avantageusement la suivante :The weight composition of the main constituents is advantageously as follows:
. carbonate alcalino-terreux 30 à 95% . matière réfractaire 70 à 5%. alkaline earth carbonate 30 to 95%. refractory material 70 to 5%
. liant 0 à 15%,. binding 0 to 15%,
FEUILLE DE REMPLACEMENT Les proportions optimales dépendront de l'effet recherché. Plus la proportion de carbonate alcalino- terreux est élevée, plus l'effet épurant sera important. Inversement, plus la proportion de matière réfractaire est élevée, plus la résistance à l'érosion du revêtement sera importante.REPLACEMENT SHEET The optimal proportions will depend on the desired effect. The higher the proportion of alkaline earth carbonate, the greater the purifying effect. Conversely, the higher the proportion of refractory material, the greater the resistance to erosion of the coating.
Il y a cependant avantage à ce que la proportion de matière réfractaire soit tout juste suffisante pour conférer au revêtement la résistance à l'érosion désirée de façon à préserver les propriétés épurantes dues à l'oxyde alcalino-terreux subsistant après libération du CO2. Afin d'accroître les propriétés épurantes du revêtement, on privilégiera dans la composition les éléments contenant du calcium. Dans certains cas, la présence du liant n'est pas obligatoire, car un effet de prise à l'eau existe déjà en son absence.There is however an advantage in that the proportion of refractory material is just sufficient to give the coating the desired resistance to erosion so as to preserve the purifying properties due to the alkaline earth oxide remaining after release of the CO2. In order to increase the purifying properties of the coating, the elements containing calcium will be favored in the composition. In some cases, the presence of the binder is not compulsory, because a setting effect with water already exists in its absence.
Les meilleurs résultats sont obtenus avec la composition suivante : . 60 à 80% de dolomie crueThe best results are obtained with the following composition:. 60 to 80% raw dolomite
. 10 à 40% 'de matière réfractaire ; et l à 5% de liant. Le carbonate alcalino-terreux peut être du carbonate de calcium pur ou associé à un autre carbonate, par exemple du carbonate de magnésium, sous forme de dolomie.. 10 to 40% ' of refractory material; and 1 to 5% of binder. The alkaline earth carbonate can be pure calcium carbonate or combined with another carbonate, for example magnesium carbonate, in the form of dolomite.
Par ailleurs, les oxydes alcalino-terreux cités à titre d'exemples de matière réfractaire peuvent être remplacés en tout ou partie par des hydroxydes et/ou des sulfates, ces derniers étant transformés en oxydes lors de la cuisson.Furthermore, the alkaline earth oxides cited as examples of refractory material can be replaced in whole or in part by hydroxides and / or sulphates, the latter being transformed into oxides during cooking.
De préférence, les grains de la matière réfractaire ont au moins en partie une dimension supérieure à celle des grains de carbonates et/ou d' ydroxydes et/ou de sulfates alcalino-terreux.Preferably, the grains of the refractory material have at least partly a dimension greater than that of the grains of carbonates and / or hydroxides and / or alkaline earth sulfates.
FEUILLE DE REMPLACEMENT En effet, les grains de carbonates, d'hydroxydes et de sulfates se décomposent d'autant plus facilement et rapidement qu'ils sont plus petits.REPLACEMENT SHEET In fact, the grains of carbonates, hydroxides and sulfates decompose the more easily and quickly the smaller they are.
De façon générale, on peut régler la granulometrie en fonction du résultat recherché, à savoir la porosité qui confère des propriétés isolantes et/ou de frittage qui assure la cohésion et la résistance à 1 ' érosion.In general, the particle size can be adjusted as a function of the desired result, namely the porosity which gives insulating and / or sintering properties which ensures cohesion and resistance to erosion.
La composition selon l'invention renferme en outre de préférence jusqu'à 20% en poids de fibres organiques et/ou minérales.The composition according to the invention also preferably contains up to 20% by weight of organic and / or mineral fibers.
La composition selon l'invention peut également renfermer une matière carbonée en grains .The composition according to the invention may also contain a carbonaceous matter in grains.
De préférence, la composition renferme en outre jusqu'à 5% en poids d'un agent tensio-actif.Preferably, the composition additionally contains up to 5% by weight of a surfactant.
La composition précitée peut être appliquée sur le fond et les faces latérales d'un répartiteur de coulée, par projection ou moulage en une ou plusieurs couches de quelques centimètres d'épaisseur. Dans le cas où l'on veut accélérer l'apparition du frittage à la surface de la couche épurante lors de son premier contact avec l'acier liquide, on pourra utilement ajouter au mélange un ou plusieurs fondants tels que, par exemple : de l'olivine, de la colémanite, de la borocalcite (borate de calcium), de l'oxyde de fer, un fluorure, de l'acide borique et ses sels (borax) et leurs mélanges. On peut ainsi choisir un fondant qui migre vers la surface avec l'eau lors du séchage, tel que de l'acide borique, par exemple, pour obtenir un frittage rapide de la surface qui vient au contact de l'acier liquide, et rechercher un frittage moins rapide ou moins actif dans la masse du revêtement épurant grâce à un fondant qui ne migre pas tel que, par exemple, de la colémanite. La finesse des grains constituant le revêtement joue également un rôle dans le processus du frittage, et on peut avantageusement utiliser les formules suivantes, les pourcentages étant donnés en poids :The aforementioned composition can be applied to the bottom and the lateral faces of a tundish, by spraying or molding in one or more layers a few centimeters thick. In the case where it is desired to accelerate the appearance of sintering on the surface of the purifying layer during its first contact with the liquid steel, it is useful to add to the mixture one or more fluxes such as, for example: olivine, colemanite, borocalcite (calcium borate), iron oxide, fluoride, boric acid and its salts (borax) and their mixtures. We can thus choose a flux which migrates towards the surface with water during drying, such as boric acid, for example, to obtain a rapid sintering of the surface which comes into contact with liquid steel, and seek a slower or less active sintering in the mass of the purifying coating thanks to a flux which does not migrate such as, for example, colemanite. The fineness of the grains constituting the coating also plays a role in the sintering process, and the following formulas can advantageously be used, the percentages being given by weight:
Dolomie et/ou calcite et/ou hydroxydes et/ou sulfates : 30 à 95%, diamètre des grains < 3 mm, de préférence < 1 mmDolomite and / or calcite and / or hydroxides and / or sulfates: 30 to 95%, grain diameter <3 mm, preferably <1 mm
Matière réfractaire : 70 à 5%, diamètre des grains < 5 mm, de préférence < 2 mm Liant : 0 à 15% Carbone : 0 à 5%Refractory material: 70 to 5%, grain diameter <5 mm, preferably <2 mm Binder: 0 to 15% Carbon: 0 to 5%
Fondants : 0 à 10% On pourra choisir comme fondant, suivant le casFondants: 0 to 10% You can choose as fondant, depending on the case
- un fondant facilement soluble, susceptible de migrer vers la surface,- an easily soluble flux, capable of migrating to the surface,
- un fondant peu ou pas soluble,- a poorly or not soluble fondant,
- un mélange des deux types de fondants dans une proportion prédéterminée permettant un certain frittage sélectif en surface et dans les différentes épaisseurs de la couche.- a mixture of the two types of fluxes in a predetermined proportion allowing a certain selective sintering on the surface and in the different thicknesses of the layer.
On peut en outre obtenir une compacité maximale de la couche en optimisant les granulometries respectives des différents constituants de façon connue, par exemple grâce à l'application de la loi de Bolomey ou de la compacité Fumas ou encore grâce à la règle du triangle : on peut ainsi augmenter la résistance de la couche épurante à 1 ' érosion par le métal liquide sans avoir à utiliser un procédé quelconque de compactage mécanique irréalisable en pratique à peu de frais. Dans le cas d'un revêtement en plusieurs couches, la composition et la granulometrie des grains peuvent varier d'une couche à l'autre en fonction des propriétés recherchées.It is also possible to obtain a maximum compactness of the layer by optimizing the respective particle sizes of the various constituents in a known manner, for example by applying the Bolomey law or the Fumas compactness or else by virtue of the triangle rule: can thus increase the resistance of the purifying layer to erosion by liquid metal without having to use any mechanical compaction process which is impracticable in practice at low cost. In the case of a coating in several layers, the composition and the particle size of the grains can vary from one layer to another depending on the desired properties.
Ainsi, si l'on veut que la couche intérieure (celle destinée à venir en contact avec le métal liquide) ait une grande résistance à l'érosion, celle-ciThus, if we want the inner layer (the one intended to come into contact with the liquid metal) to have a high resistance to erosion, it
VEUILLE DE REMPLACEMENT renfermera davantage de matière réfractaire, et contiendra des particules fines pour favoriser le frittage.REPLACEMENT PLEASE will contain more refractory material, and will contain fine particles to promote sintering.
A l'inverse, on pourra préférer que la couche extérieure adjacente au revêtement réfractaire permanent fritte moins que la couche intérieure, de façon à pouvoir la détacher facilement du revêtement permanent en fin de coulée.Conversely, it may be preferable for the outer layer adjacent to the permanent refractory lining to sinter less than the inner layer, so that it can be easily detached from the permanent lining at the end of casting.
De même, on pourra privilégier la basicité de la couche intérieure par une forte teneur en calcium pour obtenir des propriétés épurantes optimales.Likewise, the basicity of the inner layer may be favored by a high calcium content in order to obtain optimal purifying properties.
Un revêtement en plusieurs couches pour protéger la paroi intérieure d'un récipient métallurgique peut ainsi comporter : - une couche intérieure épurante d'usure venant au contact de l'acier liquide, à base d'oxyde d'un métal alcalino-terreux (dolomie, hydroxydes, sulfates, calcite, carbonates) ,A coating in several layers to protect the interior wall of a metallurgical container can thus comprise: - an interior purifying layer of wear coming into contact with liquid steel, based on oxide of an alkaline earth metal (dolomite , hydroxides, sulfates, calcite, carbonates),
- une couche extérieure de sécurité, mise en place entre la couche épurante d'usure et le revêtement permanent ; cette couche peut être, soit une couche frittable aux températures en jeu, à base de grains d'oxydes réfractaires stables (par exemple à base de magnésie et/ou de silice et/ou d'alumine et/ou de zircon et/ou de zircone) , soit en variante une couche extérieure peu ou très peu frittable de sécurité à base d'oxydes réfractaires stables additionnés de carbone (moins de 35% de carbone) . Cette dernière couche peut également jouer le rôle de troisième couche peu ou très peu frittable mise en place entre la couche précitée de sécurité et le revêtement permanent pour éviter tout accrochage du revêtement permanent, comme toute autre couche partiellement, peu ou très peu frittable.- an external safety layer, placed between the purifying wear layer and the permanent coating; this layer may be either a sinterable layer at the temperatures involved, based on stable refractory oxide grains (for example based on magnesia and / or silica and / or alumina and / or zircon and / or zirconia), or alternatively an outer layer with little or very little sinterability of security based on stable refractory oxides added with carbon (less than 35% carbon). This last layer can also play the role of a third layer with little or very little sinterability placed between the aforementioned safety layer and the permanent coating to avoid any clinging of the permanent coating, like any other partially, little or very little sinterable layer.
On peut ainsi, par exemple, prendre pour la (ou les) couche(s) extérieure (s) de sécurité, les compositions indiquées respectivement dans les brevetsIt is thus possible, for example, to take for the outer layer (s) of security, the compositions indicated respectively in the patents
FEUILLE DE REMPLACEMENT français n° 2 393 637 et 2 585 273 au nom de la demanderesse.REPLACEMENT SHEET French No. 2,393,637 and 2,585,273 in the name of the plaintiff.
On peut également, dans le cas de trois couches, avoir une première couche intérieure épurante, une seconde couche peu ou très peu frittable ou pas frittable, et une troisième couche extérieure frittable ou au moins partiellement frittable. It is also possible, in the case of three layers, to have a first purifying inner layer, a second layer with little or very little sinterability or not sinterability, and a third outer sintering layer or at least partially sinterable.

Claims

REVENDICATIONS 1. Procédé pour revêtir la paroi intérieure d'un récipient métallurgique par un revêtement épurant à base d'oxyde d'un métal alcalino-terreux, caractérisé par les étapes suivantes :CLAIMS 1. Method for coating the interior wall of a metallurgical vessel with a purifying coating based on oxide of an alkaline earth metal, characterized by the following steps:
- on applique sur la paroi intérieure du récipient une composition renfermant au moins un carbonate simple ou multiple de métal alcalino-terreux additionné d'une certaine proportion de matière réfractaire en grains, eta composition is applied to the inner wall of the container containing at least one simple or multiple carbonate of alkaline earth metal added with a certain proportion of refractory material in grains, and
- on chauffe ce revêtement pour éliminer le CO2 et éventuellement l'eau de constitution et/ou d'hydratation et obtenir une couche du ou des oxydes de métal alcalino-terreux de structure poreuse, la proportion de matière réfractaire étant suffisante pour conférer au revêtement une résistance suffisante à l'érosion du métal liquide coulé dans le récipient.- This coating is heated to remove the CO2 and possibly the water of constitution and / or hydration and to obtain a layer of the alkaline earth metal oxide (s) of porous structure, the proportion of refractory material being sufficient to give the coating sufficient resistance to erosion of the liquid metal poured into the container.
2. Procédé conforme à la revendication 1, caractérisé en ce que la composition est projetée sous forme de boue aqueuse.2. Method according to claim 1, characterized in that the composition is sprayed in the form of aqueous mud.
3. Procédé conforme à la revendication 1, caractérisé en ce que la composition est coulée entre la surface intérieure du récipient et une paroi formant moule. 3. Method according to claim 1, characterized in that the composition is poured between the inner surface of the container and a wall forming a mold.
4. Procédé conforme à l'une des revendications4. Method according to one of claims
1 à 3, caractérisé en ce que le revêtement est chauffé à coeur aux environs de 900°C.1 to 3, characterized in that the coating is heated to the core around 900 ° C.
5. Procédé conforme à l'une des revendications 1 à 4, caractérisé en ce qu'on applique, avant le revêtement épurant, au moins une première couche d'un matériau réfractaire à base d'oxydes réfractaires stables, ce matériau étant susceptible de fritter au moins partiellement aux températures en jeu.5. Method according to one of claims 1 to 4, characterized in that at least one first layer of a refractory material based on stable refractory oxides is applied, before the purifying coating, this material being capable of sinter at least partially at the temperatures involved.
6. Composition pour la mise en oeuvre du procédé conforme à la revendication 1, caractérisée en ce que ledit carbonate alcalino-terreux est choisi parmi les composés suivants : dolomie crue, calcite et leurs mélanges.6. Composition for implementing the method according to claim 1, characterized in that said alkaline earth carbonate is chosen from following compounds: raw dolomite, calcite and their mixtures.
7. Composition conforme à la revendication 6, caractérisée en ce que la composition utilisée renferme en outre un liant choisi parmi les liants minéraux, organiques, hydrauliques et leur mélange.7. Composition according to Claim 6, characterized in that the composition used additionally contains a binder chosen from mineral, organic, hydraulic binders and their mixture.
8. Composition conforme à l'une des revendications 6 ou 7, caractérisée en ce que la matière réfractaire est choisie parmi les composés suivants : - dolomie calcinée, chaux, magnésie, chrome- magnésie, oxyde de chrome, silicate de zirconium, silice, silico-alu ineux et leurs mélanges.8. Composition according to either of Claims 6 or 7, characterized in that the refractory material is chosen from the following compounds: - calcined dolomite, lime, magnesia, chromium-magnesia, chromium oxide, zirconium silicate, silica, silico-aluminum and their mixtures.
9. Composition conforme à l'une des revendications 6 à 8, caractérisée en ce qu'elle présente la composition pondérale suivante :9. Composition according to one of claims 6 to 8, characterized in that it has the following weight composition:
. carbonate alcalino-terreux : 30 à 95% . matière réfractaire : 70 à 5% . liant : 0 à 15%.. alkaline earth carbonate: 30 to 95%. refractory material: 70 to 5%. binder: 0 to 15%.
10. Composition conforme à la revendication 9, caractérisée en ce qu'elle renferme, en poids :10. Composition according to claim 9, characterized in that it contains, by weight:
. 60 à 80% de dolomie crue . 10 à 40% de matière réfractaire et l à 5% de liant.. 60 to 80% raw dolomite. 10 to 40% of refractory material and 1 to 5% of binder.
11. Composition conforme à l'une des revendications 6 à 10, caractérisée en ce que les grains de la matière réfractaire ont au moins en partie une dimension supérieure à celle des grains de carbonate alcalino-terreux.11. Composition according to one of claims 6 to 10, characterized in that the grains of the refractory material have at least partly a dimension greater than that of the grains of alkaline earth carbonate.
12. Composition conforme à l'une des revendications 6 à 11, caractérisée en ce qu'elle renferme en outre jusqu'à 20% en poids de fibres organiques et/ou minérales.12. Composition according to one of claims 6 to 11, characterized in that it also contains up to 20% by weight of organic and / or mineral fibers.
13. Composition conforme à l'une des revendications 6 à 12, caractérisée en ce qu'elle renferme en outre jusqu'à 5% en poids d'un agent tensio- actif. 13. Composition according to one of claims 6 to 12, characterized in that it also contains up to 5% by weight of a surfactant.
14. Composition conforme à l'une des revendications 6 à 13 , caractérisée en ce qu'elle contient en outre une certaine proportion d'hydroxyde(s) alcalino-terreux et/ou d'oxyde (s) alcalino-terreux susceptibles de s'hydrater lors du mouillage de la composition, et/ou de sulfates alcalino-terreux.14. Composition according to one of claims 6 to 13, characterized in that it also contains a certain proportion of alkaline earth hydroxide (s) and / or alkaline earth oxide (s) capable of s hydrate during wetting of the composition, and / or alkaline earth sulfates.
15. Composition conforme à l'une des revendications 6 à 14, caractérisée en ce qu'elle renferme en outre de 0 à 10% en poids d'un fondant. 15. Composition according to one of claims 6 to 14, characterized in that it additionally contains from 0 to 10% by weight of a flux.
16. Composition conforme à la revendication 15, caractérisée en ce que le fondant est choisi parmi l'olivine, la colémanite, la borocalcite (borate de calcium) , l'oxyde de fer, des fluorures, l'acide borique et ses sels (borax) et leurs mélanges. 16. Composition according to claim 15, characterized in that the flux is chosen from olivine, colemanite, borocalcite (calcium borate), iron oxide, fluorides, boric acid and its salts ( borax) and their mixtures.
17. Composition conforme à l'une des revendications 15 ou 16, caractérisée en ce qu'elle renferme un fondant facilement soluble.17. Composition according to either of Claims 15 or 16, characterized in that it contains an easily soluble flux.
18. Composition conforme à l'une des revendications 6 à 17 , caractérisée en ce qu'elle présente la composition pondérale suivante :18. Composition according to one of claims 6 to 17, characterized in that it has the following weight composition:
. dolomie et/ou calcite et/ou hydroxydes et/ou sulfates : 30 à 95%. dolomite and / or calcite and / or hydroxides and / or sulfates: 30 to 95%
. grains réfractaires : 70 à 5%. refractory grains: 70 to 5%
. liant : 0 à 15% . carbone : 0 à 5%. binder: 0 to 15%. carbon: 0 to 5%
. fondant : 0 à 10%.. fondant: 0 to 10%.
19. Composition conforme à l'une des revendications 6 à 18, caractérisée en ce que les constituants principaux ont la granulometrie suivante : - carbonates, hydroxydes, oxydes et sulfates de métaux alcalino-terreux : diamètre inférieur à 3 mm, et de préférence inférieur à 1 mm,19. Composition according to one of claims 6 to 18, characterized in that the main constituents have the following particle size distribution: - carbonates, hydroxides, oxides and sulfates of alkaline earth metals: diameter less than 3 mm, and preferably less at 1 mm,
- grains réfractaires : diamètre inférieur à 5 mm, et de préférence inférieur à 2 mm. - refractory grains: diameter less than 5 mm, and preferably less than 2 mm.
20. Composition conforme à l'une des revendications 6 à 19, caractérisée en ce que les20. Composition according to one of claims 6 to 19, characterized in that the
FEUILLE DE REMPLACEMENT granulometries respectives des différents constituants sont choisies de manière à donner au revêtement épurant une compacité maximale.REPLACEMENT SHEET Respective particle sizes of the various constituents are chosen so as to give the purifying coating maximum compactness.
21. Revêtement pour protéger la paroi intérieure d'un récipient métallurgique, ce revêtement étant obtenu par la mise en oeuvre du procédé conforme à la revendication 5, caractérisé en ce qu'il comporte successivement :21. Coating to protect the inner wall of a metallurgical container, this coating being obtained by implementing the method according to claim 5, characterized in that it successively comprises:
- une couche intérieure épurante destinée à venir en contact avec le métal liquide, cette couche étant réalisée au moyen d'une composition conforme à l'une quelconque des revendications 6 à 20 ;- a purifying inner layer intended to come into contact with the liquid metal, this layer being produced by means of a composition according to any one of Claims 6 to 20;
- au moins une couche extérieure frittable ou au moins partiellement frittable aux températures en jeu, cette couche étant à base d'oxydes réfractaires stables.- At least one sinterable outer layer or at least partially sinterable at the temperatures involved, this layer being based on stable refractory oxides.
FEUILLE DE REMPLACEMENT REPLACEMENT SHEET
EP90907138A 1989-04-12 1990-04-11 Process for coating a metallurgical container with a purifying layer and composition relating thereto, and protective coating thus obtained Expired - Lifetime EP0422192B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90907138T ATE99199T1 (en) 1989-04-12 1990-04-11 PROCESS AND COMPOSITION FOR LINING A METALLURGICAL VESSEL BY MEANS OF A CLEANING LINING AND LINING THUS MANUFACTURED.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8904822A FR2648066B1 (en) 1989-04-12 1989-04-12 PROCESS FOR COATING A METALLURGICAL CONTAINER WITH A PURIFYING COATING AND COMPOSITION RELATING THERETO
FR8904822 1989-04-12

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EP0422192A1 true EP0422192A1 (en) 1991-04-17
EP0422192B1 EP0422192B1 (en) 1993-12-29

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US (1) US5188794A (en)
EP (1) EP0422192B1 (en)
KR (1) KR960005886B1 (en)
AU (1) AU628557B2 (en)
BR (1) BR9006411A (en)
CA (1) CA2030522A1 (en)
CS (1) CS179790A3 (en)
DE (1) DE69005578T2 (en)
ES (1) ES2047930T3 (en)
FR (1) FR2648066B1 (en)
HU (1) HU904442D0 (en)
WO (1) WO1990011853A1 (en)

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FR2683220B1 (en) * 1991-11-04 1994-05-20 Sollac PROCESS FOR COATING A CONTINUOUS CASTING DISTRIBUTOR WITH REFRACTORY MATERIAL, DISTRIBUTOR AND REFRACTORY MATERIAL RESULTING FROM THE IMPLEMENTATION OF THIS PROCESS.
US5314599A (en) * 1992-07-28 1994-05-24 Alcan International Limited Barrier layer against fluoride diffusion in linings of aluminum reduction cells
US5507474A (en) * 1994-01-13 1996-04-16 Minerals Technologies, Inc. Lining for molten metal handling vessles
US5643350A (en) * 1994-11-08 1997-07-01 Vectra Technologies, Inc. Waste vitrification melter
AUPS329202A0 (en) * 2002-07-01 2002-07-18 Cast Centre Pty Ltd Coatings for articles used with molten metal
JP4410796B2 (en) * 2004-03-15 2010-02-03 黒崎播磨株式会社 Continuous casting nozzle
CN115448701B (en) * 2022-08-19 2023-04-14 山西太钢不锈钢股份有限公司 Magnesium-calcium refractory material for AOD smelting nickel-based alloy and preparation method thereof

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GB527024A (en) * 1939-03-28 1940-10-01 Pierre Imbert Improvements in or relating to basic refractory materials
DE966136C (en) * 1951-05-28 1957-07-11 Veitscher Magnesitwerke Ag Process for the production of highly refractory, basic insulating bricks
DE1218923B (en) * 1959-04-23 1966-06-08 Rheinische Kalksteinwerke Process for the production of highly porous, refractory, basic lightweight bricks
DE1239226B (en) * 1961-01-05 1967-04-20 Dolomitwerke Gmbh Process for the production of porous moldings from dolomite and / or magnesite
DE1239266B (en) * 1962-04-28 1967-04-27 Basf Ag Process for dyeing and / or printing textile goods
US4400335A (en) * 1981-12-15 1983-08-23 Hoganas Ab Process for repairing refractory linings
JPS6133743A (en) * 1984-07-25 1986-02-17 Kobe Steel Ltd Construction of plate-shaped refractories

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ES2047930T3 (en) 1994-03-01
AU5551790A (en) 1990-11-05
DE69005578D1 (en) 1994-02-10
CS179790A3 (en) 1992-09-16
EP0422192B1 (en) 1993-12-29
KR960005886B1 (en) 1996-05-03
HUT60173A (en) 1992-08-28
KR920700081A (en) 1992-02-19
FR2648066B1 (en) 1994-04-01
WO1990011853A1 (en) 1990-10-18
CA2030522A1 (en) 1990-10-13
DE69005578T2 (en) 1994-04-28
AU628557B2 (en) 1992-09-17
HU904442D0 (en) 1992-08-28
FR2648066A1 (en) 1990-12-14
BR9006411A (en) 1991-08-06
US5188794A (en) 1993-02-23

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