EP1352099B1 - Method for avoiding drag-in of zinc particles on galvanized sheet metal - Google Patents

Method for avoiding drag-in of zinc particles on galvanized sheet metal Download PDF

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Publication number
EP1352099B1
EP1352099B1 EP02711660A EP02711660A EP1352099B1 EP 1352099 B1 EP1352099 B1 EP 1352099B1 EP 02711660 A EP02711660 A EP 02711660A EP 02711660 A EP02711660 A EP 02711660A EP 1352099 B1 EP1352099 B1 EP 1352099B1
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EP
European Patent Office
Prior art keywords
chute
zinc
bath
panels
carbon
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EP02711660A
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German (de)
French (fr)
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EP1352099A1 (en
Inventor
Michel Dubois
Michel Tombu
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ArcelorMittal France SA
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Arcelor France SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—Apparatus
    • C23C2/0034—Details related to elements immersed in bath
    • C23C2/00348—Fixed work supports or guides

Definitions

  • the present invention relates to a novel process for avoiding or controlling the entrainment of zinc-containing solid compounds, in the form of oxides and / or clods, floating on the surface of the liquid, in hot-dip coating. a steel sheet by dipping in a galvanizing bath.
  • the invention also relates to the device for implementing the method.
  • This problem induces unacceptable defects for the customer when a very high surface quality is required, as is for example the case of the skin parts of automobile bodies.
  • These particles may be for example compounds of Fe 2 Al 5 , Al 2 O 3 , ZnO or a mixture thereof in combination with metallic zinc.
  • the observed point defects generally have a surface of less than 6 mm 2 but they can be arranged in "strings", that is to say form a series of local defects more or less aligned in the direction of travel of the sheet.
  • the document JP-A-63 086852 proposes a method for suppressing the generation of steam and the formation of a uniform film on the surface of the liquid metal bath.
  • floating calcium silicate bodies of round or spherical shape which are chemically inert and not very wettable, are provided at said surface. It is thus possible to isolate the bath of liquid metal from the atmosphere of the continuous annealing furnace. This solution is however not satisfactory since, by construction, these floating bodies of the ceramic ball type are always in direct contact with the sheet, which can generate defects as well as the premature wear of said balls.
  • the document EP-A-0 060 225 discloses a method and an installation for the coating of hot dipped yarns in vertical strand.
  • the installation comprises successively a pretreatment unit (cleaning, pickling, drying), a preheating unit, the actual coating unit including a vertical chute containing the molten metal and finally a cooling unit coated wire.
  • the inside of the chute is covered with a refractory material that can not be wetted by the liquid metal.
  • the lower opening for the entry of the wire into the chute is equipped with a tubular connector covered with an internal refractory sleeve which extends to the wetting line and which consists of a non-wettable material.
  • the liquid metal for example alumina.
  • the object of this invention is to wrap the wire with a protective gas at the inlet and the outlet of the chute.
  • the thread to be coated can not be compared to a flat product such as a two-dimensional strip (typically thickness / width ratio). from 5 to 1000). Indeed, in this case, problems of flatness of the non-rigid strip arise and the cross section in a chute must be perfectly controlled.
  • the present invention aims to provide a chute, which by construction prevents zinc particles from accumulating at the wetting line.
  • An additional object of the invention is to provide a solution compatible with existing chutes or requiring only minor modifications thereof.
  • a further aim of the invention is to provide a simple and inexpensive solution.
  • the present invention relates to a chute, of substantially rectangular and elongate section, for the entry in the downward direction of a steel sheet previously annealed in a bath of liquid metal preferably containing zinc, in the context of a method of coating by hot dipping, the inlet of the bath being preferably in a reducing atmosphere, or mentally non-oxidizing for iron, said atmosphere being brought to a temperature in the range defined by the average temperature of said bath ⁇ 50 ° C, characterized in that the inner part of said chute is covered, in whole or in part, at the level of the wetting line of the liquid metal, by plates made of a material non-wettable vis-à-vis said bath and disposed at least at each of the longer sides of the chute, on either side of said steel sheet.
  • said chute has a substantially rectangular section and said non-wettable means are arranged only at the longer side of the chute, located on the side of the steel sheet where the inner surface of the said chute forms a substantially acute angle with the wetting surface.
  • said means are plates based on carbon or ceramic.
  • said means are plates consisting of a material coated with carbon, ceramic or a non-wettable material by liquid zinc.
  • said material not wettable by liquid zinc is a molybdenum-tungsten alloy.
  • said carbon-based plates comprise graphite, sintered carbon, impregnated or not, or fiber-reinforced carbon.
  • said plates are mechanically fixed to said chute directly by means of bolts.
  • said plates are mechanically fixed to said chute by means of screwed or welded angles.
  • said ceramic plates consist of a single piece machined in the mass or consist of several pieces assembled or nested.
  • Another aspect of the present invention relates to a method for preventing the entrainment of particles preferably containing zinc on a steel sheet, previously annealed under a reducing atmosphere or virtually non-oxidizing for iron, in a coating plant.
  • hot dipping steel having an inlet trough according to the first aspect of the present invention, characterized in that it comprises a step of downward penetration of said sheet into a bath of metal, preferably zinc melted in the presence of particles of salts or oxides of zinc or other metals, said particles floating at the wetting line during the course of the process but without adhesion to said sheet or to the inner surface of said chute .
  • Figure 1 shows schematically a sectional view of a galvanized steel trunking type installation, according to the state of the art.
  • Figures 2.a and 2.b show schematically the contact angle of a drop of a respectively wet and non-wetting liquid with a horizontal flat surface.
  • Figure 3. schematically shows a sectional view of a first embodiment of galvanizing steel trunking, according to the invention.
  • Figure 3.b schematically shows a sectional view of a second embodiment of galvanizing steel trunking, according to the invention.
  • FIG. 4 represents the detail of a first embodiment of the ceramic plates according to the invention.
  • Figure 5 shows the detail of a second embodiment of the ceramic plates according to the invention.
  • FIG. 1 schematically shows the configuration of a conventional inlet chute 2 of a steel sheet 3 in an electroplating bath 1.
  • the defects due to entrainment of the zinc particles accumulate more particularly on the face 4.
  • the inner portion of the chute 5 above the wetting surface 6 is in a generally reducing atmosphere for iron and composed for example of hydrogen mixed with an inert gas such as nitrogen.
  • the chute is always constructed of metal, for example stainless steel, for reasons of cost, implementation and assembly, as well as to ensure airtightness.
  • the most commonly used material is therefore stainless steel, and in particular grade 316L, for its known resistance to attack by liquid zinc. This material nevertheless has the disadvantage, like any other metal, of being wetted by liquid zinc.
  • the chute is of elongated rectangular shape, with a length / width ratio at least greater than 2, and preferably greater than 5.
  • the present invention consists in making modifications to the construction of the inner part of the chute, located at the level of the wetting line.
  • the principle is to cover or protect, possibly in the form of an interposition between the bath and the chute, the inner submerged part of the chute by elements or plates 7 in non-wettable material by zinc (Figures 3.a and 3.b). Under these conditions, the zinc particles can no longer accumulate at the wetting line.
  • a wetting liquid is defined as being a liquid whose contact angle ⁇ of a droplet 10 with a given horizontal surface, wetted by this liquid, does not exceed 45.degree. oxidizing and / or reducing quenching agents for iron, even after several days of use (Figure 2.a).
  • the contact angle is greater than 45 °, the liquid is considered non-wetting ( Figure 2.b).
  • the contact angle ⁇ is itself defined as the angle formed, on the side of the drop 10, by the tangent T at the contact surface of the drop 10 with said wet horizontal surface (FIGS. 2a and 2). .b).
  • the microscopic particles whose formation is inevitable by the physico-chemistry of the process, are permanently driven by their small size and can not accumulate.
  • the elements or plates 7 used in the invention are either based on ceramic material, that is to say a combination of oxides and / or carbides, or based on carbon compounds such as graphite and its many variants, such as sintered carbon, impregnated or not, reinforced with fibers, etc.
  • Carbon is a particularly advantageous material for a preferred embodiment of the invention, insofar as, in addition to being non-wettable for liquid zinc, it makes it possible to avoid oxidation-or even to promote the reduction - from the liquid metal to the mooring line 6. In addition to possessing a reducing power well known to those skilled in the art, carbon is still anticorrosive vis-à-vis liquid metals.
  • the present invention is not limited to the examples of plate materials described but relates to any material non-wettable by zinc that can be used (sulfides, fluorides, special alloys, etc.). Thus, it is well known to those skilled in the art that molybdenum-tungsten alloys are non-wettable by zinc.
  • the atmosphere inside the chute is oxidizing for the liquid metal (while of course remaining non-oxidizing for iron), for example in the form of an injected oxidizing gas such as nitrogen or hydrogen wet, optionally supplemented with oxygen and carbon dioxide, to avoid the formation of zinc vapors above the wetting line, which promote the appearance of the aforementioned defects on the sheet.
  • an injected oxidizing gas such as nitrogen or hydrogen wet
  • oxygen and carbon dioxide optionally supplemented with oxygen and carbon dioxide
  • the gas injected into the trough must have a more oxidizing power than in the absence of these plates, typically for example a H 2 / H 2 O ratio, or equivalent.
  • (H 2 + CO) / (H 2 O + CO 2 ) preferably ranging from 5 to 25, in order to obtain the oxidation of the liquid metal at surface itself, as desired, for the purpose of preventing the formation of the vapors described above.
  • Another feature of the invention is to use a mechanical fastening of said plates 7 of ceramic or carbon.
  • This type of attachment thus allows the free expansion of the different materials relative to each other.
  • said fastener is for example of the type with screwed or welded angles 8 (FIG. 3.a) or else a direct fixation by bolts 9 (FIG. 3.b).
  • the ceramic plates can be made either in one piece with machining in the mass ( Figure 4), or in several pieces (Figure 5). These plates can be fixed against the chute or have a space with the chute, where the liquid zinc can flow freely. They may also consist of several layers of different properties, such as for example a layer reflecting heat on one side of the plate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)

Abstract

A spout for inlet of steel sheet into a bath of liquid metal containing zinc in a hot coating process, the spout being under a reducing or non-oxidizing atmosphere, is covered or protected, wholly or partially, at the liquid metal moistening level by ceramic or carbon based plates (7) rendering the inner surface non-wettable with respect to the bath. An Independent claim is included for a method for preventing the entrainment of zinc particles on a steel sheet in a galvanizing installation using this inlet spout.

Description

Objet de l'inventionObject of the invention

La présente invention se rapporte à un nouveau procédé permettant d'éviter ou de contrôler l'entraînement de composés solides contenant du zinc, sous forme d'oxydes et/ou de mottes, flottant à la surface du liquide, lors du revêtement à chaud d'une tôle d'acier par trempage dans un bain de galvanisation.The present invention relates to a novel process for avoiding or controlling the entrainment of zinc-containing solid compounds, in the form of oxides and / or clods, floating on the surface of the liquid, in hot-dip coating. a steel sheet by dipping in a galvanizing bath.

L'invention se rapporte également au dispositif pour la mise en oeuvre du procédé.The invention also relates to the device for implementing the method.

Etat de la techniqueState of the art

En galvanisation à chaud, l'entraînement de particules contenant du zinc (oxydes, sels, etc.) au sein du revêtement d'une tôle galvanisée lors de son passage dans le bain de zinc et de son essorage est en général assez fréquent.In hot-dip galvanizing, the entrainment of zinc-containing particles (oxides, salts, etc.) in the coating of a galvanized sheet during its passage in the zinc bath and its spin is in general quite frequent.

Ce problème induit des défauts rédhibitoires pour le client lorsqu'une très haute qualité de surface est requise, comme c'est par exemple le cas pour les pièces de peau des carrosseries automobiles.This problem induces unacceptable defects for the customer when a very high surface quality is required, as is for example the case of the skin parts of automobile bodies.

Des études relatives à la caractérisation de ces particules ont montré qu'il pouvait s'agir par exemple de composés de Fe2Al5, Al2O3, ZnO ou d'un mélange de ceux-ci en combinaison avec du zinc métallique. Les défauts ponctuels observés présentent généralement une surface de moins de 6 mm2 mais ils peuvent être disposés en "chapelets", c'est-à-dire former une série de défauts locaux plus ou moins alignés dans le sens de défilement de la tôle.Studies relating to the characterization of these particles have shown that they may be for example compounds of Fe 2 Al 5 , Al 2 O 3 , ZnO or a mixture thereof in combination with metallic zinc. The observed point defects generally have a surface of less than 6 mm 2 but they can be arranged in "strings", that is to say form a series of local defects more or less aligned in the direction of travel of the sheet.

L'examen des conditions de galvanisation a montré que l'apparition des défauts en question résulte de l'entraînement brutal dans le zinc liquide d'amas de particules flottant à la surface du bain, au niveau de la zone de mouillage de la tôle, nettoyée et réduite par les processus amont. Cette zone est appelée par l'homme de l'art "sabot" ou "joint liquide".Examination of the galvanizing conditions has shown that the occurrence of the defects in question results from the sudden entrainment in the liquid zinc of particle masses floating on the surface of the bath, at the wetting zone of the sheet, cleaned and reduced by upstream processes. This area is known to those skilled in the art as "hoof" or "liquid seal".

Ces particules flottantes viennent soit des mattes formées dans le bain et qui remontent à la surface de par leur plus faible densité, soit de l'oxydation de la surface libre du bain de zinc, malgré la présence d'hydrogène dans la goulotte (également appelée trompe).These floating particles come either mattes formed in the bath and back to the surface by their lower density, or the oxidation of the free surface of the zinc bath, despite the presence of hydrogen in the chute (also called deceived).

L'expérience a permis d'observer les points suivants :

  • les défauts sont plus nombreux sur la face de la tôle en contact avec le rouleau immergé, qui est généralement appelé rouleau de fond. Ladite face correspond également à l'endroit où l'angle formé par la surface interne de la goulotte et la surface du bain est essentiellement aigu. Cet angle aigu induit des conditions favorables d'entraînement des particules ;
  • les défauts apparaissent généralement par "paquets", lorsqu'en particulier la surface du zinc est agitée. Ce remous se produit par exemple en présence d'une mauvaise planéité de bande, de démattage de la surface à l'air libre ou encore lorsqu'on procède au chargement d'un lingot de zinc ;
  • le remous décrit ci-dessus induit un décollement de particules au niveau de.la ligne de mouillage. Celles-ci ne peuvent sortir de la zone confinée de la goulotte que par entraînement sur la tôle ;
  • ce décollement des particules ne présente un défaut, lors des utilisations ultérieures du produit, que si les particules présentes finalement sur la tôle sont de taille suffisante.
Experience has shown the following:
  • the defects are more numerous on the face of the sheet in contact with the immersed roll, which is generally called bottom roll. Said face also corresponds to the place where the angle formed by the inner surface of the chute and the surface of the bath is essentially acute. This acute angle induces favorable conditions for driving the particles;
  • the defects generally appear as "packets" when, in particular, the zinc surface is agitated. This eddy occurs for example in the presence of a bad band flatness, removal of the surface in the open air or when loading a zinc ingot;
  • the eddy described above induces a delamination of particles at the wetting line. These can only leave the confined area of the chute by driving on the sheet;
  • this delamination of the particles has a defect, during subsequent uses of the product, if the particles finally present on the sheet are of sufficient size.

Dans le but de réduire la surface d'évaporation du zinc, on a proposé l'utilisation d'objets en céramique flottant à la surface du bain de zinc liquide et recouvrant au moins en partie sa surface.In order to reduce the evaporation surface of zinc, it has been proposed to use ceramic objects floating on the surface of the liquid zinc bath and covering at least part of its surface.

Le document JP-A-63 086852 propose un procédé visant à supprimer la génération de vapeur et la formation d'un film uniforme à la surface du bain de métal liquide. Pour ce faire, on dispose à ladite surface des corps solides flottants en silicate de calcium, de forme ronde ou sphérique, chimiquement inertes et peu mouillables. On peut ainsi isoler le bain de métal liquide de l'atmosphère du four de recuit continu. Cette solution n'est toutefois pas satisfaisante vu que, par construction, ces corps flottants de type billes céramique sont toujours en contact direct avec la tôle, ce qui peut générer des défauts ainsi que l'usure prématurée desdites billes.The document JP-A-63 086852 proposes a method for suppressing the generation of steam and the formation of a uniform film on the surface of the liquid metal bath. For this purpose, floating calcium silicate bodies of round or spherical shape, which are chemically inert and not very wettable, are provided at said surface. It is thus possible to isolate the bath of liquid metal from the atmosphere of the continuous annealing furnace. This solution is however not satisfactory since, by construction, these floating bodies of the ceramic ball type are always in direct contact with the sheet, which can generate defects as well as the premature wear of said balls.

Certains ont essayé de revêtir la face intérieure de la goulotte par des projections diverses sur celle-ci et entre autres céramiques. Ces traitements sont difficiles à réaliser parfaitement vu l'espace confiné lié à la faible ouverture de la pièce. En outre, ils subissent généralement un écaillage à cause, soit de leur porosité, soit de la forte dilatation différentielle entre,le métal support, par exemple de l'inox austénitique, et la matière projetée.Some have tried to coat the inside of the chute with various projections on it and among other ceramics. These treatments are difficult to achieve perfectly given the confined space related to the small opening of the room. In addition, they generally undergo peeling because of either their porosity or the high differential expansion between the support metal, for example austenitic stainless steel, and the projected material.

On a encore proposé des méthodes pour l'extraction des impuretés de surface du bain utilisant des dispositifs tels que des pompes.Methods for the extraction of surface impurities from the bath using devices such as pumps have also been proposed.

Le document EP-A-0 060 225 décrit un procédé et une installation pour le revêtement de fils au trempé à chaud en brin vertical. L'installation comporte successivement une unité de prétraitement (nettoyage, décapage, séchage), une unité de préchauffage, l'unité de revêtement proprement dite dont une goulotte verticale contenant le métal fondu et enfin une unité de refroidissement du fil revêtu. L'intérieur de la goulotte est recouvert d'un matériau réfractaire non mouillable par le métal liquide. De plus, l'ouverture inférieure pour l'entrée du fil dans la goulotte est équipé d'un connecteur tubulaire recouvert d'un manchon réfractaire interne qui s'étend jusqu'à la ligne de mouillage et qui consiste en un matériau non mouillable par le métal liquide, par exemple de l'alumine. L'objet de cette invention est d'envelopper le fil d'un gaz protecteur à l'entrée et à la sortie de la goulotte.The document EP-A-0 060 225 discloses a method and an installation for the coating of hot dipped yarns in vertical strand. The installation comprises successively a pretreatment unit (cleaning, pickling, drying), a preheating unit, the actual coating unit including a vertical chute containing the molten metal and finally a cooling unit coated wire. The inside of the chute is covered with a refractory material that can not be wetted by the liquid metal. In addition, the lower opening for the entry of the wire into the chute is equipped with a tubular connector covered with an internal refractory sleeve which extends to the wetting line and which consists of a non-wettable material. the liquid metal, for example alumina. The object of this invention is to wrap the wire with a protective gas at the inlet and the outlet of the chute.

Le problème posé par l'état de la technique est fondamentalement différent de celui que se propose de résoudre la présente invention.The problem posed by the state of the art is fundamentally different from that proposed by the present invention.

D'abord, au niveau de la géométrie du produit, le fil à revêtir, de par nature monodimensionnel sur sa longueur et isotrope sur sa section, ne peut être comparé à un produit plat tel qu'une bande bidimensionnelle (rapport épaisseur/largeur typiquement de 5 à 1000). En effet, dans ce cas, des problèmes de planéité de la bande non rigide se posent et la section de passage transversale dans une goulotte doit être parfaitement maîtrisée.First, at the level of the geometry of the product, the thread to be coated, by its nature monodimensional over its length and isotropic on its section, can not be compared to a flat product such as a two-dimensional strip (typically thickness / width ratio). from 5 to 1000). Indeed, in this case, problems of flatness of the non-rigid strip arise and the cross section in a chute must be perfectly controlled.

D'autre part, il faut tenir compte du sens de circulation du produit à revêtir. Dans le document cité, celui-ci est vertical vers le haut en entrée et en sortie. Il s'ensuit la nécessité d'empêcher des fuites de métal liquide vers le bas et d'assurer l'adhérence des particules de revêtement, ce qui est défavorisé par les forces de gravité. Pour s'opposer à celles-ci, on utilise donc la pression du gaz et des forces additionnelles de mouillage. Dans le cadre du revêtement au trempé d'une bande d'acier, l'entrée de la bande dans le bain est descendante et la sortie est montante, après déflexion sur le rouleau de fond. Il n'y a donc pas les mêmes contraintes de gravité à l'entrée.On the other hand, it is necessary to take into account the direction of circulation of the product to be coated. In the document cited, it is vertical upward in and out. It follows the need to prevent leakage of liquid metal downwards and to ensure the adhesion of the coating particles, which is disadvantaged by the forces of gravity. To oppose them, one therefore uses the pressure of the gas and additional forces of wetting. As part of the dip coating of a steel strip, the entrance of the strip into the bath is down and the output is rising after deflection on the bottom roller. So there is not the same gravity constraints at the input.

Buts de l'inventionGoals of the invention

La présente invention vise à fournir une goulotte, qui par construction, empêche les particules de zinc de s'accumuler à la ligne de mouillage.The present invention aims to provide a chute, which by construction prevents zinc particles from accumulating at the wetting line.

Un but complémentaire de l'invention est de fournir une solution compatible avec les goulottes existantes ou ne demandant que des modifications peu importantes de celles-ci..An additional object of the invention is to provide a solution compatible with existing chutes or requiring only minor modifications thereof.

Un but encore complémentaire de l'invention est de fournir une solution simple et peu onéreuse.A further aim of the invention is to provide a simple and inexpensive solution.

Principaux éléments caractéristiques de l'inventionMain characteristic elements of the invention

La présente invention se rapporte à une goulotte, de section essentiellement rectangulaire et allongée, pour l'entrée dans le sens descendant d'une tôle d'acier préalablement recuite dans un bain de métal liquide contenant de préférence du zinc, dans le cadre d'un procédé de revêtement par trempage à chaud, l'entrée du bain étant de préférence sous une atmosphère réductrice, ou franchement non-oxydante pour le fer, ladite atmosphère étant portée à une température située dans l'intervalle défini par la température moyenne dudit bain ± 50 °C, caractérisée en ce que la partie interne de ladite goulotte est recouverte, en tout ou en partie, au niveau de la ligne de mouillage du métal liquide, par des plaques en un matériau non mouillable vis-à-vis dudit bain et disposées au moins au niveau de chacun des côtés de plus grande longueur de la goulotte, de part et d'autre de ladite tôle d'acier.The present invention relates to a chute, of substantially rectangular and elongate section, for the entry in the downward direction of a steel sheet previously annealed in a bath of liquid metal preferably containing zinc, in the context of a method of coating by hot dipping, the inlet of the bath being preferably in a reducing atmosphere, or frankly non-oxidizing for iron, said atmosphere being brought to a temperature in the range defined by the average temperature of said bath ± 50 ° C, characterized in that the inner part of said chute is covered, in whole or in part, at the level of the wetting line of the liquid metal, by plates made of a material non-wettable vis-à-vis said bath and disposed at least at each of the longer sides of the chute, on either side of said steel sheet.

Selon une deuxième forme d'exécution préférentielle, ladite goulotte présente une section essentiellement rectangulaire et lesdits moyens non mouillables sont disposés uniquement au niveau du côté de plus grande longueur de la goulotte, sis du côté de la tôle d'acier où la surface interne de ladite goulotte forme un angle essentiellement aigu avec la surface de mouillage.According to a second preferred embodiment, said chute has a substantially rectangular section and said non-wettable means are arranged only at the longer side of the chute, located on the side of the steel sheet where the inner surface of the said chute forms a substantially acute angle with the wetting surface.

Avantageusement, lesdits moyens sont des plaques à base de carbone ou de céramique.Advantageously, said means are plates based on carbon or ceramic.

De manière particulièrement avantageuse, lesdits moyens sont des plaques constituées d'une matière recouverte de carbone, de céramique ou d'un matériau non mouillable par le zinc liquide.Particularly advantageously, said means are plates consisting of a material coated with carbon, ceramic or a non-wettable material by liquid zinc.

Toujours avantageusement, ledit matériau non mouillable par le zinc liquide est un alliage de molybdène-tungstène.Still advantageously, said material not wettable by liquid zinc is a molybdenum-tungsten alloy.

De manière particulièrement avantageuse, lesdites plaques à base de carbone comprennent du graphite, du carbone fritté, imprégné ou non, ou du carbone renforcé de fibres.Particularly advantageously, said carbon-based plates comprise graphite, sintered carbon, impregnated or not, or fiber-reinforced carbon.

Selon une réalisation préférentielle du dispositif de l'invention, lesdites plaques sont fixées mécaniquement à ladite goulotte directement au moyen de boulons.According to a preferred embodiment of the device of the invention, said plates are mechanically fixed to said chute directly by means of bolts.

Selon une autre réalisation préférentielle du dispositif de l'invention, lesdites plaques sont fixées mécaniquement à ladite goulotte au moyen de cornières vissées ou soudées.According to another preferred embodiment of the device of the invention, said plates are mechanically fixed to said chute by means of screwed or welded angles.

De préférence, lesdites plaques en céramique sont constituées d'une seule pièce usinée dans la masse ou sont constituées de plusieurs pièces assemblées ou emboîtées.Preferably, said ceramic plates consist of a single piece machined in the mass or consist of several pieces assembled or nested.

Un autre aspect de la présente invention concerne un procédé pour éviter l'entraînement de particules contenant de préférence du zinc sur une tôle d'acier, préalablement recuite sous une atmosphère réductrice ou franchement non-oxydante pour le fer, dans une installation de revêtement d'acier par trempage à chaud, présentant une goulotte d'entrée selon le premier aspect de la présente invention, caractérisé en ce qu'il comprend une étape de pénétration dans le sens descendant de ladite tôle dans un bain de métal, de préférence de zinc, fondu, en présence de particules de sels ou d'oxydes de zinc ou d'autres métaux, lesdites particules flottant à la ligne de mouillage au cours du déroulement du procédé mais sans adhésion ni à ladite tôle ni à la surface interne de ladite goulotte.Another aspect of the present invention relates to a method for preventing the entrainment of particles preferably containing zinc on a steel sheet, previously annealed under a reducing atmosphere or frankly non-oxidizing for iron, in a coating plant. hot dipping steel, having an inlet trough according to the first aspect of the present invention, characterized in that it comprises a step of downward penetration of said sheet into a bath of metal, preferably zinc melted in the presence of particles of salts or oxides of zinc or other metals, said particles floating at the wetting line during the course of the process but without adhesion to said sheet or to the inner surface of said chute .

Brève description des figuresBrief description of the figures

La figure 1 représente schématiquement une vue en coupe d'une installation de type goulotte de galvanisation d'acier, selon l'état de la technique.Figure 1 shows schematically a sectional view of a galvanized steel trunking type installation, according to the state of the art.

Les figures 2.a et 2.b représentent schématiquement l'angle de contact d'une goutte d'un liquide respectivement mouillant et non mouillant avec une surface plane horizontale.Figures 2.a and 2.b show schematically the contact angle of a drop of a respectively wet and non-wetting liquid with a horizontal flat surface.

La figure 3.a représente schématiquement une vue en coupe d'un première forme d'exécution de goulotte de galvanisation d'acier, selon l'invention.Figure 3.a schematically shows a sectional view of a first embodiment of galvanizing steel trunking, according to the invention.

La figure 3.b représente schématiquement une vue en coupe d'une deuxième forme d'exécution de goulotte de galvanisation d'acier, selon l'invention.Figure 3.b schematically shows a sectional view of a second embodiment of galvanizing steel trunking, according to the invention.

La figure 4 représente le détail d'une première forme d'exécution des plaques en céramique selon l'invention.FIG. 4 represents the detail of a first embodiment of the ceramic plates according to the invention.

La figure 5 représente le détail d'une deuxième forme d'exécution des plaques en céramique selon l'invention.Figure 5 shows the detail of a second embodiment of the ceramic plates according to the invention.

Description d'une forme d'exécution préférée de l'inventionDescription of a preferred embodiment of the invention

La figure 1 montre schématiquement la configuration d'une goulotte classique 2 d'entrée d'une tôle d'acier 3 dans un bain de galvanisation 1. Les défauts dus à l'entraînement des particules de zinc s'accumulent plus particulièrement sur la face arrière 4. La partie interne de la goulotte 5 au-dessus de la surface de mouillage 6 se trouve sous atmosphère généralement réductrice pour le fer et composée par exemple d'hydrogène mélangé à un gaz inerte tel que l'azote.FIG. 1 schematically shows the configuration of a conventional inlet chute 2 of a steel sheet 3 in an electroplating bath 1. The defects due to entrainment of the zinc particles accumulate more particularly on the face 4. The inner portion of the chute 5 above the wetting surface 6 is in a generally reducing atmosphere for iron and composed for example of hydrogen mixed with an inert gas such as nitrogen.

La goulotte est toujours construite en métal, par exemple en acier inoxydable, pour des raisons de coûts, de mise en oeuvre et d'assemblage, ainsi que pour garantir l'étanchéité à l'air ambiant. La matière la plus communément utilisée est donc l'acier inoxydable, et en particulier la nuance 316L, pour sa résistance connue à l'attaque par le zinc liquide. Cette matière a néanmoins l'inconvénient, comme tout métal d'ailleurs, d'être mouillée par le zinc liquide. La goulotte est de forme rectangulaire allongée, avec un rapport longueur/largeur au moins supérieur à 2, et de préférence supérieur à 5.The chute is always constructed of metal, for example stainless steel, for reasons of cost, implementation and assembly, as well as to ensure airtightness. The most commonly used material is therefore stainless steel, and in particular grade 316L, for its known resistance to attack by liquid zinc. This material nevertheless has the disadvantage, like any other metal, of being wetted by liquid zinc. The chute is of elongated rectangular shape, with a length / width ratio at least greater than 2, and preferably greater than 5.

La présente invention consiste à apporter des modifications à la construction de la partie interne de la goulotte, se trouvant au niveau de la ligne de mouillage.The present invention consists in making modifications to the construction of the inner part of the chute, located at the level of the wetting line.

Le principe est de recouvrir ou protéger, éventuellement sous forme d'une interposition entre le bain et la goulotte, la partie immergée intérieure de la goulotte par des éléments ou plaques 7 en matière non mouillable par le zinc (figures 3.a et 3.b). Dans ces conditions, les particules de zinc ne peuvent plus s'accumuler à la ligne de mouillage.The principle is to cover or protect, possibly in the form of an interposition between the bath and the chute, the inner submerged part of the chute by elements or plates 7 in non-wettable material by zinc (Figures 3.a and 3.b). Under these conditions, the zinc particles can no longer accumulate at the wetting line.

Dans le cadre de l'invention, on définit un liquide mouillant comme étant un liquide dont l'angle de contact θ d'une goutte 10 avec une surface horizontale donnée, mouillée par ce liquide, n'excède pas 45°, dans des conditions de trempe oxydantes et/ou réductrices pour le fer, même après plusieurs jours d'utilisation (figure 2.a). Lorsque l'angle de contact est supérieur à 45°, le liquide est considéré comme non-mouillant (figure 2.b). L'angle de contact θ est lui-même défini comme étant l'angle formé, du côté de la goutte 10, par la tangente T à la surface de contact de la goutte 10 avec ladite surface horizontale mouillée (figures 2.a et 2.b).In the context of the invention, a wetting liquid is defined as being a liquid whose contact angle θ of a droplet 10 with a given horizontal surface, wetted by this liquid, does not exceed 45.degree. oxidizing and / or reducing quenching agents for iron, even after several days of use (Figure 2.a). When the contact angle is greater than 45 °, the liquid is considered non-wetting (Figure 2.b). The contact angle θ is itself defined as the angle formed, on the side of the drop 10, by the tangent T at the contact surface of the drop 10 with said wet horizontal surface (FIGS. 2a and 2). .b).

Ainsi, lors du défilement de la tôle, les particules microscopiques, dont la formation est inévitable de par la physico-chimie du procédé, sont entraînées en permanence de par leur petite taille et ne peuvent s'accumuler.Thus, during the scrolling of the sheet, the microscopic particles, whose formation is inevitable by the physico-chemistry of the process, are permanently driven by their small size and can not accumulate.

Les éléments ou plaques 7 utilisés dans l'invention sont soit à base de matière céramique, c'est-à-dire une combinaison d'oxydes et/ou de carbures, soit à base de composés en carbone tels que le graphite et ses nombreuses variantes, telles que carbone fritté, imprégné ou non, renforcé de fibres, etc.The elements or plates 7 used in the invention are either based on ceramic material, that is to say a combination of oxides and / or carbides, or based on carbon compounds such as graphite and its many variants, such as sintered carbon, impregnated or not, reinforced with fibers, etc.

Le carbone est un matériau particulièrement avantageux pour un exemple de réalisation préférée de l'invention, dans la mesure où, en plus d'être non mouillable pour le zinc liquide, il permet d'éviter l'oxydation -ou encore de favoriser la réduction- du métal liquide à la ligne de mouillage 6. Outre le fait de posséder un pouvoir réducteur bien connu de l'homme de l'art, le carbone est encore anticorrosif vis-à-vis des métaux liquides.Carbon is a particularly advantageous material for a preferred embodiment of the invention, insofar as, in addition to being non-wettable for liquid zinc, it makes it possible to avoid oxidation-or even to promote the reduction - from the liquid metal to the mooring line 6. In addition to possessing a reducing power well known to those skilled in the art, carbon is still anticorrosive vis-à-vis liquid metals.

La présente invention ne se limite pas aux exemples de matériaux de plaques décrits mais concerne toute matière non mouillable par le zinc pouvant être utilisée (sulfures, fluorures, alliages spéciaux, etc.). Ainsi, il est bien connu de l'homme de l'art que les alliages molybdène-tungstène sont non mouillables par le zinc.The present invention is not limited to the examples of plate materials described but relates to any material non-wettable by zinc that can be used (sulfides, fluorides, special alloys, etc.). Thus, it is well known to those skilled in the art that molybdenum-tungsten alloys are non-wettable by zinc.

On impose généralement que l'atmosphère à l'intérieur de la goulotte soit oxydante pour le métal liquide (tout en restant bien sûr non-oxydante pour le fer), par exemple sous la forme d'un gaz oxydant injecté tel que azote ou hydrogène humide, complété éventuellement d'oxygène et de dioxyde de carbone, afin d'éviter la formation de vapeurs de zinc au-dessus de la ligne de mouillage, qui favorisent l'apparition des défauts précités sur la tôle. Vu le caractère réducteur des plaques de carbone utilisées dans l'invention, on observe une plus grande consommation en agent oxydant (O2 ou H2O ou CO2) par rapport au cas classique dans l'état de la technique où ces éléments sont absents.It is generally imposed that the atmosphere inside the chute is oxidizing for the liquid metal (while of course remaining non-oxidizing for iron), for example in the form of an injected oxidizing gas such as nitrogen or hydrogen wet, optionally supplemented with oxygen and carbon dioxide, to avoid the formation of zinc vapors above the wetting line, which promote the appearance of the aforementioned defects on the sheet. Given the reducing nature of the carbon plates used in the invention, a greater consumption of oxidizing agent (O 2 or H 2 O or CO 2 ) is observed compared to the conventional case in the state of the art where these elements are absent.

Ainsi une production de CO est observée, conduisant à un redépôt de carbone et qui n'a d'ailleurs aucun effet néfaste sur le produit aux teneurs mesurées, à savoir entre 10 et 300 ppm, pour lesquelles la carburation des tôles d'acier ne peut se produire de manière significative.Thus CO production is observed, leading to carbon redeposition and which has no adverse effect on the product at the measured levels, namely between 10 and 300 ppm, for which the carburation of the steel sheets does not can occur significantly.

Il résulte de cette consommation, en présence de plaques réductrices 7, que le gaz injecté dans la goulotte doit avoir un pouvoir plus oxydant qu'en l'absence de ces plaques, typiquement par exemple un rapport H2/H2O, ou équivalent (H2+CO)/(H2O+CO2), variant de préférence de 5 à 25, afin d'obtenir l'oxydation du métal liquide à la surface même, tel que désiré, dans le but de prévenir la formation des vapeurs décrites précédemment.As a result of this consumption, in the presence of reducing plates 7, the gas injected into the trough must have a more oxidizing power than in the absence of these plates, typically for example a H 2 / H 2 O ratio, or equivalent. (H 2 + CO) / (H 2 O + CO 2 ), preferably ranging from 5 to 25, in order to obtain the oxidation of the liquid metal at surface itself, as desired, for the purpose of preventing the formation of the vapors described above.

Une autre caractéristique de l'invention est d'utiliser une fixation mécanique desdites plaques 7 de céramique ou carbone. Ce type de fixation permet ainsi la libre dilatation des différents matériaux les uns par rapport aux autres. Plus précisément, ladite fixation est par exemple de type à cornières vissées ou soudées 8 (figure 3.a) ou encore une fixation directe par boulons 9 (figure 3.b).Another feature of the invention is to use a mechanical fastening of said plates 7 of ceramic or carbon. This type of attachment thus allows the free expansion of the different materials relative to each other. More precisely, said fastener is for example of the type with screwed or welded angles 8 (FIG. 3.a) or else a direct fixation by bolts 9 (FIG. 3.b).

Par ailleurs, les plaques de céramique peuvent être réalisées soit d'une seule pièce avec usinage dans la masse (figure 4), soit en plusieurs pièces (figure 5). Ces plaques peuvent être fixées contre la goulotte ou présenter un espace avec la goulotte, où le zinc liquide peut circuler librement. Elles peuvent encore être constituées de plusieurs couches de propriétés différentes, comme par exemple une couche réfléchissant la chaleur sur une face de la plaque.Furthermore, the ceramic plates can be made either in one piece with machining in the mass (Figure 4), or in several pieces (Figure 5). These plates can be fixed against the chute or have a space with the chute, where the liquid zinc can flow freely. They may also consist of several layers of different properties, such as for example a layer reflecting heat on one side of the plate.

Claims (11)

  1. Chute (2) of essentially rectangular and elongate cross section, for introducing a pre-annealed steel sheet (3) downwards into a bath of liquid metal preferably containing zinc (1), in the context of a hot-dip coating process, characterized in that the internal part of the said chute (2) is covered, entirely or partially, at the liquid-metal wetting line (6), with panels (7) of a material that cannot be wetted by the said bath and that are positioned at least at each of the longest sides of the chute (2), on each side of the said steel sheet (3).
  2. Chute according to Claim 1, characterized in that the said non-wettable panels (7) are positioned only along the longest side of the chute (2) which lies on that side (4) of the steel sheet where the internal surface of the said chute (2) makes an essentially acute angle with the liquid metal wetting surface (6).
  3. Chute according to Claim 1 or 2, characterized in that the said panels (7) are based on carbon or on ceramic.
  4. Chute according to Claim 1 or 2, characterized in that the said panels (7) are made of a material covered with carbon, with ceramic, or with a material that cannot be wetted by the liquid zinc.
  5. Chute according to Claim 4, characterized in that the said material that cannot be wetted by the liquid zinc is a molybdenum-tungsten alloy.
  6. Chute according to Claim 3, characterized in that the said carbon-based panels (7) contain graphite, sintered carbon, which may or may not be impregnated, or fibre-reinforced carbon.
  7. Chute according to any one of Claims 3 to 6, characterized in that the said panels (7) are mechanically attached to the said chute directly using bolts (9).
  8. Chute according to any one of Claims 3 to 6, characterized in that the said panels (7) are mechanically attached to the said chute by means of screwed-on or welded-on brackets (8).
  9. Chute according to any one of Claims 3 to 6, characterized in that the said panels (7) are made as a single piece machined from solid or consist of several pieces assembled or nested together.
  10. Process for avoiding the entrainment of particles, preferably containing zinc, onto a steel sheet (3), pre-annealed under a reducing atmosphere or atmosphere that is decidedly non-oxidizing with respect to iron, in an installation for hot-dip coating steel, having an inlet chute (2) according to any one of the preceding claims, characterized in that it comprises a step whereby the said sheet (3) in a downwards movement enters a bath (1) of molten metal, preferably zinc, in the presence of particles of salts or oxides of zinc or other metals, the said particles floating along the wetting line (6) as the process is performed, but without these particles adhering either to the said sheet or to the internal surface of the said chute.
  11. Process according to Claim 10, characterized in that the entrance to the bath is under a reducing atmosphere, or atmosphere that is decidedly non-oxidizing with respect to iron, the said atmosphere being raised to a temperature that lies in the range defined by the mean temperature of the said bath ± 50°C.
EP02711660A 2001-01-17 2002-01-16 Method for avoiding drag-in of zinc particles on galvanized sheet metal Expired - Lifetime EP1352099B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02711660A EP1352099B1 (en) 2001-01-17 2002-01-16 Method for avoiding drag-in of zinc particles on galvanized sheet metal

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP01870010A EP1225245A1 (en) 2001-01-17 2001-01-17 Process for preventing the entrainment of zinc particles on a galvanized sheet
EP01870010 2001-01-17
PCT/BE2002/000006 WO2002057505A1 (en) 2001-01-17 2002-01-16 Method for avoiding drag-in of zinc particles on galvanized sheet metal
EP02711660A EP1352099B1 (en) 2001-01-17 2002-01-16 Method for avoiding drag-in of zinc particles on galvanized sheet metal

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EP1352099A1 EP1352099A1 (en) 2003-10-15
EP1352099B1 true EP1352099B1 (en) 2007-11-14

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EP02711660A Expired - Lifetime EP1352099B1 (en) 2001-01-17 2002-01-16 Method for avoiding drag-in of zinc particles on galvanized sheet metal

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AT (1) ATE378437T1 (en)
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JPS6058787B2 (en) * 1981-03-10 1985-12-21 興国鋼線索株式会社 High-speed dip coating method and device for linear bodies
JPS6386852A (en) * 1986-09-30 1988-04-18 Sumitomo Metal Ind Ltd Continuous hot dip metal coating device
JPH01294851A (en) * 1988-05-23 1989-11-28 Kobe Steel Ltd Method for preventing generation of dross in snout
JPH0499852A (en) * 1990-08-15 1992-03-31 Kawasaki Steel Corp Production of hot-dip galvanized steel sheet or galvannealed steel sheet
JPH0762512A (en) * 1993-08-19 1995-03-07 Daido Steel Co Ltd Method for decreasing amount of zinc vapor in snout for zinc-aluminum alloy plating
JPH07145463A (en) * 1993-11-24 1995-06-06 Nippon Steel Corp Method and device for hot dip metal coating
JPH07145464A (en) * 1993-11-24 1995-06-06 Nippon Steel Corp Method and device for hot dip metal coating
JPH07252619A (en) * 1994-03-11 1995-10-03 Nisshin Steel Co Ltd Continuous hot-dip alloy coating device for steel strip
JP3492759B2 (en) * 1994-03-22 2004-02-03 株式会社フジコー Hot metal plating bath immersion member
JP3352541B2 (en) * 1994-09-12 2002-12-03 川崎製鉄株式会社 Continuous hot-dip galvanizing method and apparatus for steel sheet
EP0828864A1 (en) * 1995-05-29 1998-03-18 M3D Société Anonyme Method and apparatus for coating a metal strip with a metal or alloy with a lower melting or liquidus point than the strip material

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EP1352099A1 (en) 2003-10-15
EP1225245A1 (en) 2002-07-24
DE60223492D1 (en) 2007-12-27
ATE378437T1 (en) 2007-11-15
ES2294119T3 (en) 2008-04-01
DE60223492T2 (en) 2008-11-27
WO2002057505A1 (en) 2002-07-25

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