EP0037143B1 - Hot dip coating process - Google Patents

Hot dip coating process Download PDF

Info

Publication number
EP0037143B1
EP0037143B1 EP81200313A EP81200313A EP0037143B1 EP 0037143 B1 EP0037143 B1 EP 0037143B1 EP 81200313 A EP81200313 A EP 81200313A EP 81200313 A EP81200313 A EP 81200313A EP 0037143 B1 EP0037143 B1 EP 0037143B1
Authority
EP
European Patent Office
Prior art keywords
zinc
bath
baths
aluminium alloy
products
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81200313A
Other languages
German (de)
French (fr)
Other versions
EP0037143A1 (en
Inventor
Jacques Pelerin
Dimitri Coutsouradis
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.)
Centre de Recherches Metallurgiques CRM ASBL
Original Assignee
Centre de Recherches Metallurgiques CRM ASBL
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from BE6/47114A external-priority patent/BE882430A/en
Priority claimed from BE6/47184A external-priority patent/BE883725A/en
Priority claimed from BE6/47183A external-priority patent/BE883724A/en
Application filed by Centre de Recherches Metallurgiques CRM ASBL filed Critical Centre de Recherches Metallurgiques CRM ASBL
Publication of EP0037143A1 publication Critical patent/EP0037143A1/en
Application granted granted Critical
Publication of EP0037143B1 publication Critical patent/EP0037143B1/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon

Definitions

  • the present invention relates to a method of hot coating a material of any shape in semi-calm steel, calm or alloyed with silicon.
  • the process which is the subject of the present description is applicable in all cases where several successive molten metal baths are used to form a zinc coating with a high aluminum content on the said material, both in the context of the coating with hot so that during continuous processes.
  • Zn-AI coating consists of passing the fluxed sheet through a first Zn bath, then into a lead bath, then only into a liquid bath. of Zn-AI, so as to form the desired coating of Zn-AI alloy.
  • the installations constructed for the implementation of these methods generally comprise a tank separated into two parts by a transverse partition, provided in its lower part, with means to allow the passage from one side to the other of the partition, of the material. treat. It is thus normal to find at the bottom of the tank, over its entire base section, a lead bath of height greater than the passage means provided in the partition, and, supernatant on the lead bath, but separated by this same partition, on the one hand a practically pure zinc bath and on the other hand a zinc bath containing about 10% of aluminum.
  • the sheet to be treated enters the curve, on one side of the transverse partition, passes successively into the bath of practically pure zinc, into the lead bath and, after passing the other side of the partition, exits through the Zn-AI alloy bath, which gives the desired coating layer.
  • This method is mainly applied in the case of Zn-1 0% AI alloys, i.e. coating baths for which the temperatures erasures in use are close to those of traditional galvanizing baths, because the melting temperatures of the materials constituting the baths located on either side of the partition are almost identical.
  • the use of this type of process is no longer possible in the case of zinc alloys with a high aluminum content, in particular in the case of alloys having a melting point higher than that of traditional galvanizing baths, located around 440-460 ° C.
  • British patent GB-A-337,399 relates to a process for coating steel strips by immersion in several successive baths, in particular of zinc and then of aluminum or of zinc containing 3 to 20% of aluminum.
  • the aluminum or zinc-aluminum bath causes the zinc coating to melt and be eliminated, and its replacement respectively by aluminum or zinc-aluminum.
  • English patent GB-A-876,032 discloses a process for the formation of two successive layers of coating, consisting respectively of zinc and a zinc-aluminum alloy.
  • the subject of the present invention is precisely a process using several successive metal baths and making it possible to produce, on silicon steel materials, coatings which do not have the drawbacks mentioned above.
  • the invention relates to a process for hot coating a material of any shape in semi-calm steel, calm or alloyed with silicon, in which the said material is immersed in a first bath essentially consisting of zinc or a first zinc-aluminum alloy, then in a second bath essentially consisting of a second zinc-aluminum alloy, said first and second bath being at different temperatures.
  • a first variant of this process is characterized in that at least one of the so-called zinc-aluminum alloy baths has an aluminum content of between 3% and 10% and in that at least Sb elements are added thereto , Ce, Mg, La, Sn, in a content not exceeding 0.5% by weight.
  • the method of the invention is characterized in that at least one of the so-called zinc-aluminum alloy baths has an aluminum content of less than or equal to 10% and in that magnesium is added to it in a content not exceeding 10% by weight.
  • the method of the invention is characterized in that at least one of said baths of zinc-aluminum alloy has an aluminum content of between 20% and 80% and in that it is added to it silicon and magnesium, each in a content not exceeding 3% by weight.
  • the material to be treated which may be hot, is immersed in said first bath for a duration of less than 3 minutes, and in the second bath for a duration less than 20 minutes, and the duration of stay of the material in the second bath is preferably at least equal to its stay in the first bath.
  • the method of the invention makes it possible to minimize the influence of the quality of the surface preparation of the material, while making it possible to obtain coatings of constant thickness and satisfactory adhesion on silicon steel materials.
  • This favorable behavior is due to the formation of a multilayer coating which has a multi-phase metallic outer layer composed of phases enriched in at least two different metals, the number of phases enriched in a given metal being advantageously greater than one.
  • intermetallic layers containing in particular iron or consisting of a determined metal (hereinafter called M t ), while the polyphase surface layer comprises metal M "as well as one or more other metals (hereinafter called M 2 ... M ”) forming with M, and / or between them the different phases mentioned above.

Landscapes

  • 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)

Description

La présente invention a trait à un procédé de revêtement à chaud d'un matériau de forme quelconque en acier semi-calmé, calmé ou allié au silicium.The present invention relates to a method of hot coating a material of any shape in semi-calm steel, calm or alloyed with silicon.

Le procédé, objet de la présente description, est d'application dans tous les cas où l'on emploie plusieurs bains métalliques fondus successifs pour former un revêtement de zinc à haute teneur en aluminium sur le dit matériau, tant dans le cadre du revêtement à chaud à façon, qu'au cours de processus continus.The process which is the subject of the present description is applicable in all cases where several successive molten metal baths are used to form a zinc coating with a high aluminum content on the said material, both in the context of the coating with hot so that during continuous processes.

Dans le but de montrer plus clairement l'intérêt de l'invention, la description qui suit sera axée sur le revêtement par trempé de tôles ou de tubes d'acier au silicium dans des bains de zinc et d'alliages Zn-AI, uniquement à titre d'exemple et sans que cela doit restrictif à ce type de matériau.In order to show more clearly the interest of the invention, the following description will focus on the dip coating of silicon steel sheets or tubes in baths of zinc and Zn-AI alloys, only by way of example and without this being restrictive to this type of material.

Les processus usuels de revêtement par trempé, tels que la galvanisation au trempé d'un laminé, par exemple une tôle ou un tube en acier, se déroulent ordinairement en deux phases, à savoir:

  • - une phase, dite de préparation, qui consiste à débarrasser la surface de la tôle du tube de tout ce qui pourrait nuire à l'obtention d'un produit galvanisé satisfaisant, par exemple graisse, cambouis, poussières, etc..., ce qui se fait généralement par une opération de dégraissage suivie d'un rinçage, d'un décapage, d'un nouveau rinçage et d'un fluxage (sec ou humide). Dans la majorité des processus continus, dans le cas des tôles, cette opération est réalisée en faisant passer le matériau considéré dans une enceinte où règne une atmosphère gazeuse, essentiellement réductrice.
  • - une phase qui consiste à tremper le matériau ainsi préparé dans un bain de zinc liquide à une température le plus souvent comprise entre 440°C et 460°C, pendant une durée appropriée.
The usual dip coating processes, such as dip galvanizing of a laminate, for example a steel sheet or tube, usually take place in two phases, namely:
  • - a phase, called preparation, which consists in ridding the surface of the sheet metal of the tube of all that could harm the obtaining of a satisfactory galvanized product, for example grease, sludge, dust, etc. which is generally done by a degreasing operation followed by rinsing, pickling, rinsing again and fluxing (dry or wet). In the majority of continuous processes, in the case of sheets, this operation is carried out by passing the material under consideration through an enclosure in which there is a gaseous, essentially reducing, atmosphere.
  • - A phase which consists in dipping the material thus prepared in a bath of liquid zinc at a temperature usually between 440 ° C and 460 ° C, for an appropriate period.

Les opérations dont il est question ci-dessus ayant trait au dégraissage, décapage et fluxage, ont été surtout élaborées pour des installations de revêtement à chaud au trempé dans lesquelles le bain métallique liquide est composé de zinc pratiquement pur, à l'exception des impuretés habituelles.The operations referred to above relating to degreasing, pickling and fluxing, were especially developed for hot dip coating installations in which the liquid metal bath is composed of practically pure zinc, with the exception of impurities usual.

Ces dernières années, on a assisté au développement de revêtements au trempé, composés notamment d'alliages Zn-AI, qui ont connu un succès certain en raison d'un certain nombre d'avantages au point de vue de la résistance à la corrosion, par rapport au revêtement au trempé dans le zinc ou d'autres métaux non alliés.In recent years, we have witnessed the development of dip coatings, in particular composed of Zn-AI alloys, which have been successful due to a number of advantages from the point of view of corrosion resistance, compared to dip coating in zinc or other unalloyed metals.

Dans le cas d'une préparation de surface utilisée dans la galvanisation à façon conventionnelle ou dans la galvanisation de tubes ou de tôles dans des bains de galvanisation traditionnels, et caractérisée par un dégraissage, un décapage et un fluxage, des problèmes majeurs apparaissent sous la forme de défauts, tels que manques de matière dans le revêtement de galvanisation, en raison de la présence d'additifs, tels que l'aluminium dans le bain de revêtement. Ces défauts sont dus principalement à une réaction entre les agents fluxants et les éléments d'addition au bain métallique de revêtement, et en particulier l'aluminium.In the case of a surface preparation used in conventional galvanizing or in the galvanizing of tubes or sheets in traditional galvanizing baths, and characterized by degreasing, pickling and fluxing, major problems appear under the form of defects, such as lack of material in the galvanizing coating, due to the presence of additives, such as aluminum in the coating bath. These defects are mainly due to a reaction between the fluxing agents and the additive elements to the metallic coating bath, and in particular aluminum.

Dans le cas particulier important des aciers semi-calmés, calmés ou alliés au silicium, on a en outre constaté que le procédé classique de galvanisation conduisait à l'apparition de suré- paisseurs sur le matériau, à un aspect gris mat du revêtement, à une faible adhérence et à des inégalités dans la formation des sous-couches intermétalliques, ce qui pouvait conduire à la mise au rebut des pièces galvanisées.In the important particular case of semi-quenched, quenched or silicon-alloyed steels, it has also been found that the conventional galvanizing process leads to the appearance of thickenings on the material, to a matt gray appearance of the coating, to poor adhesion and unevenness in the formation of intermetallic undercoats, which could lead to the scrapping of galvanized parts.

La mise en oeuvre de revêtements à base d'alliages de Zn, AI et autres a nécessité la conception de nouvelles lignes de traitement sous atmosphères fort élaborées ou du moins, la transformation coûteuse de lignes existantes, de manière à obtenir une préparation de surface adaptée à ces nouveaux alliages de revêtement. Ces nouveaux bains métalliques d'alliages nécessitent une préparation de surface plus poussée que dans le cas d'une galvanisation classique, notamment en imposant une contrainte plus sévère, par exemple dans le cas de points de rosée plus bas.The use of coatings based on Zn, AI and other alloys necessitated the design of new treatment lines under very sophisticated atmospheres or at least the costly transformation of existing lines, so as to obtain a suitable surface preparation. to these new coating alloys. These new metal alloy baths require more extensive surface preparation than in the case of conventional galvanization, in particular by imposing a more severe stress, for example in the case of lower dew points.

Un type de procédé préconisé par plusieurs sociétés parmi lesquelles Nippon Kokan K.K., dans le cadre du revêtement Zn-AI, consiste à faire passer la tôle fluxée dans un premier bain de Zn, puis dans un bain de plomb, puis seulement dans un bain liquide de Zn-AI, de manière à former le revêtement désiré en alliage de Zn-AI.One type of process recommended by several companies, including Nippon Kokan KK, as part of the Zn-AI coating, consists of passing the fluxed sheet through a first Zn bath, then into a lead bath, then only into a liquid bath. of Zn-AI, so as to form the desired coating of Zn-AI alloy.

Les installations construites pour la mise en oeuvre de ces procédés comprennent généralement une cuve séparée en deux parties par une cloison transversale, pourvue dans sa partie inférieure, de moyens pour permettre le passage d'un côté à l'autre de la cloison, du matériau à traiter. C'est ainsi qu'il est normal de trouver au fond de la cuve, sur toute sa section de base, un bain de plomb de hauteur supérieure aux moyens de passage ménagés dans la cloison, et, surnageant sur le bain de plomb, mais séparés par cette même cloison, d'une part un bain de zinc pratiquement pur et d'autre part un bain de zinc contenant environ 10% d'aluminium. La tôle à traiter pénètre dans la curve, d'un côté de la cloison transversale, passe successivement dans le bain de zinc pratiquement pur, dans le bain de plomb et, après passage de l'autre côté de la cloison, ressort à travers le bain d'alliage Zn-AI, qui donne la couche de revêtement désirée.The installations constructed for the implementation of these methods generally comprise a tank separated into two parts by a transverse partition, provided in its lower part, with means to allow the passage from one side to the other of the partition, of the material. treat. It is thus normal to find at the bottom of the tank, over its entire base section, a lead bath of height greater than the passage means provided in the partition, and, supernatant on the lead bath, but separated by this same partition, on the one hand a practically pure zinc bath and on the other hand a zinc bath containing about 10% of aluminum. The sheet to be treated enters the curve, on one side of the transverse partition, passes successively into the bath of practically pure zinc, into the lead bath and, after passing the other side of the partition, exits through the Zn-AI alloy bath, which gives the desired coating layer.

Cette méthode est essentiellement appliquée dans le cas d'alliages Zn-1 0% AI, c'est-à-dire de bains de revêtement pour lesquels les températures d'utilisation sont proches de celles de bains de galvanisation traditionnels, car les températures de fusion des matériaux constituant les bains situés de part et d'autre de la cloison sont presque identiques. Toutefois, l'utilisation de ce type de procédé n'est plus possible dans le cas d'alliages de zinc à hauteur teneur en aluminium, notamment dans le cas d'alliages ayant un point de fusion supérieur à celui des bains de galvanisation traditionnels, situé aux alentours de 440-460°C.This method is mainly applied in the case of Zn-1 0% AI alloys, i.e. coating baths for which the temperatures erasures in use are close to those of traditional galvanizing baths, because the melting temperatures of the materials constituting the baths located on either side of the partition are almost identical. However, the use of this type of process is no longer possible in the case of zinc alloys with a high aluminum content, in particular in the case of alloys having a melting point higher than that of traditional galvanizing baths, located around 440-460 ° C.

Dans le domaine de l'utilisation de plusieurs bains successifs on connaît, par le brevet anglais GB-A-1,121,548, un procédé de traitement thermique et de galvanisation de fil dans lequel le fil, après avoir été chauffé à au moins 700°C-c'est-à-dire au-delà de point de transformation A1-est refroidi dans un bain de plomb, puis plongé dans un bain de zinc où le revêtement de plomb est éliminé et remplacé par un revêtement de zinc.In the field of the use of several successive baths, there is known from the English patent GB-A-1,121,548, a process for heat treatment and galvanizing of wire in which the wire, after having been heated to at least 700 ° C. that is to say beyond transformation point A 1 - is cooled in a lead bath, then immersed in a zinc bath where the lead coating is removed and replaced by a zinc coating.

Le brevet anglais GB-A-337,399 concerne un procédé de revêtement de bandes d'acier par immersion dans plusieurs bains successifs, notamment de zinc puis d'aluminium ou de zinc contenant 3 à 20% d'aluminium. Selon ce brevet, le bain d'aluminium ou de zinc-aluminium provoque la fusion et l'élimination du revêtement de zinc, et son remplacement respectivement par de l'aluminium ou du zinc-aluminium.British patent GB-A-337,399 relates to a process for coating steel strips by immersion in several successive baths, in particular of zinc and then of aluminum or of zinc containing 3 to 20% of aluminum. According to this patent, the aluminum or zinc-aluminum bath causes the zinc coating to melt and be eliminated, and its replacement respectively by aluminum or zinc-aluminum.

Enfin, le brevet anglais GB-A-876,032 révèle un procédé pour la formation de deux couches successives de revêtement, constituées respectivement de zinc et d'un alliage zinc-aluminium.Finally, English patent GB-A-876,032 discloses a process for the formation of two successive layers of coating, consisting respectively of zinc and a zinc-aluminum alloy.

La présente invention a précisément pour objet un procédé utilisant plusieurs bains métalliques successifs et permettant de réaliser, sur des matériaux en acier au silicium, des revêtements qui ne présentent pas les inconvénients rappelés plus haut.The subject of the present invention is precisely a process using several successive metal baths and making it possible to produce, on silicon steel materials, coatings which do not have the drawbacks mentioned above.

D'une manière générale, l'invention porte sur un procédé de revêtement à chaud d'un matériau de forme quelconque en acier semi-calmé, calmé ou allié au silicium, dans lequel on immerge le dit matériau dans un premier bain essentiellement constitué de zinc ou d'un premier alliage zinc-aluminium, puis dans un second bain essentiellement constitué d'un second alliage zinc-aluminium, les dits premier et second bain se trouvant à des températures différentes.In general, the invention relates to a process for hot coating a material of any shape in semi-calm steel, calm or alloyed with silicon, in which the said material is immersed in a first bath essentially consisting of zinc or a first zinc-aluminum alloy, then in a second bath essentially consisting of a second zinc-aluminum alloy, said first and second bath being at different temperatures.

Une première variante de ce procédé est caractérisée en ce qu'au moins un des dits bains d'alliage zinc-aluminium présente une teneur en aluminium comprise entre 3% et 10% et en ce qu'on lui ajoute au moins en des éléments Sb, Ce, Mg, La, Sn, en une teneur ne dépassant pas 0,5% en poids.A first variant of this process is characterized in that at least one of the so-called zinc-aluminum alloy baths has an aluminum content of between 3% and 10% and in that at least Sb elements are added thereto , Ce, Mg, La, Sn, in a content not exceeding 0.5% by weight.

Dans une autre variante, le procédé de l'invention est caractérisé en ce qu'au moins un des dits bains d'alliage zinc-aluminium présente une teneur en aluminium inférieure ou égale à 10% et en ce qu'on lui ajoute de magnésium en une teneur ne dépassant pas 10% en poids.In another variant, the method of the invention is characterized in that at least one of the so-called zinc-aluminum alloy baths has an aluminum content of less than or equal to 10% and in that magnesium is added to it in a content not exceeding 10% by weight.

Selon une troisième variante, le procédé de l'invention est caractérisé en ce qu'au moins un des dits bains d'alliage zinc-aluminium présente une teneur en aluminium comprise entre 20% et 80% et en ce qu'on lui ajoute du silicium et du magnésium, chacun en une teneur ne dépassant pas 3% en poids.According to a third variant, the method of the invention is characterized in that at least one of said baths of zinc-aluminum alloy has an aluminum content of between 20% and 80% and in that it is added to it silicon and magnesium, each in a content not exceeding 3% by weight.

Selon une mise en oeuvre intéressante de ces diverses variantes du procédé de l'invention, le matériau à traiter, qui peut être chaud, est immergé dans le dit premier bain pendant une durée inférieure à 3 minutes, et dans le second bain pendant une durée inférieure à 20 minutes, et la durée de séjour du matériau dans le second bain est de préférence au moins égale à sa durée de séjour dans le premier bain.According to an advantageous implementation of these various variants of the process of the invention, the material to be treated, which may be hot, is immersed in said first bath for a duration of less than 3 minutes, and in the second bath for a duration less than 20 minutes, and the duration of stay of the material in the second bath is preferably at least equal to its stay in the first bath.

Le procédé de l'invention permet de minimiser l'influence de la qualité de la préparation de surface du matériau, tout en permettant d'obtenir des revêtements d'épaisseur constante et d'adhérence satisfaisante sur des matériaux en acier au silicium.The method of the invention makes it possible to minimize the influence of the quality of the surface preparation of the material, while making it possible to obtain coatings of constant thickness and satisfactory adhesion on silicon steel materials.

Ce comportement favorable est dû à la formation d'un revêtement multicouche qui présente une couche extérieure métallique polyphasée composée de phases enrichies en au moins deux métaux différents, le nombre de phases enrichies en un métal déterminé étant avantageusement supérieur à un.This favorable behavior is due to the formation of a multilayer coating which has a multi-phase metallic outer layer composed of phases enriched in at least two different metals, the number of phases enriched in a given metal being advantageously greater than one.

Entre le substrat et la couche extérieure, peuvent se trouver une ou plusieurs couches intermétalliques contenant notamment du fer ou étant constituées d'un metal déterminé (ci-après appelé Mt), tandis que la couche superficielle polyphasée comporte du métal M" ainsi que un ou plusieurs autres métaux (ci-après appelés M2... M") formant avec M, et/ou entre eux les différentes phases précitées.Between the substrate and the outer layer, there may be one or more intermetallic layers containing in particular iron or consisting of a determined metal (hereinafter called M t ), while the polyphase surface layer comprises metal M "as well as one or more other metals (hereinafter called M 2 ... M ") forming with M, and / or between them the different phases mentioned above.

Parmi les différentes combinaisons possibles, on peut citer les cas suivants:

  • le métal M, est constitué de zinc ou d'aluminium,
  • -la couche polyphasée est constituée essentiellement de deux métaux, les autres n'intervenant pas pour plus de 5% globalement,
  • -le métal M, est du zinc et la couche polyphasée est constituée en majeure partie de zinc-aluminium,
  • - le substrat est recouvert de composés intermétalliques Fe-Zn et/ou de zinc, tandis que la couche polyphasée comporte au moins une phase enrichie en Zn et au moins une phase enrichie en AI,
  • - le substrat est recouvert de zinc contenant de 0,05% à 0,4% d'AI et au maximum 2% de Pb,
  • -la couche polyphasée est composée de zinc avec de 3% à 10% d'AI, et peut contenir au plus 0,5% globalement des éléments ci-après: Sb-Ce-Mg-La-Sn,
  • - la couche polyphasée est composée de zinc avec de l'aluminium et du magnésium, chacun de ces deux derniers éléments ne dépassant pas 10%,
  • - la couche polyphasée est composée de zinc avec de 20% à 80% d'aluminium (de préférence de 50% à 60%), et peut contenir également jusqu'à 3% de magnésium et jusqu'à 3% de silicium.
Among the different possible combinations, the following cases may be mentioned:
  • the metal M, consists of zinc or aluminum,
  • -the polyphase layer consists essentially of two metals, the others not intervening for more than 5% overall,
  • the metal M, is zinc and the polyphase layer consists mainly of zinc-aluminum,
  • the substrate is covered with intermetallic compounds Fe-Zn and / or zinc, while the polyphase layer comprises at least one phase enriched in Zn and at least one phase enriched in AI,
  • - the substrate is covered with zinc containing from 0.05% to 0.4% AI and at most 2% Pb,
  • the polyphase layer is composed of zinc with 3% to 10% of AI, and may contain at most 0.5% overall of the following elements: Sb-Ce-Mg-La-Sn,
  • - the polyphase layer is composed of zinc with aluminum and magnesium, each of these last two elements not exceeding 10%,
  • - the polyphase layer is composed of zinc with 20% to 80% aluminum (preferably from 50% to 60%), and can also contain up to 3% magnesium and up to 3% silicon.

Claims (4)

1. Hot dip coating process for products of any shape made of killed, semi-killed or silicon steel in which the said products are dipped into an initial bath made up basically of zinc or a first zinc-aluminium alloy and then into a second bath comprising basically a second zinc-aluminium alloy, the aforementioned first and second baths being at different temperatures, and which is characterized by the fact that at least one of the baths of zinc-aluminium alloy has an aluminium content of between 3% and 10% and at least one of the elements Sb, Ce, Mg, La and Sn is added to it in an amount not exceeding 0.5% by weight.
2. Hot dip coating process for products of any shape made of killed, semi-killed or silicon steel in which the said products are dipped into an initial bath made up basically of zinc or a first zinc-aluminium alloy and then into a second bath comprising basically a second zinc-aluminium alloy, the aforementioned first and second baths being at different temperatures, and which is characterized by the fact that at least one of the baths of zinc-aluminium alloy has an aluminium content of 10% or less and magnesium is added to it in an amount not exceeding 10% by weight.
3. Hot dip coating process for products of any shape made of killed, semi-killed or silicon steel in which the said products are dipped into an initial bath made up basically of zinc or a first zinc-aluminium alloy and then into a second bath comprising basically a second zinc-aluminium alloy, the aforementioned first and second baths being at different temperatures, and which is characterized by the fact that at least one of the baths of zinc-aluminium alloy has an aluminium content of between 20% and 80% and silicon and magnesium are added to it in amounts not exceeding 3% by weight for each element.
4. Process in accordance with any of claims 1 to 3 characterized by the fact that the products concerned are dipped in the first bath for less than 3 minutes and into the second bath for less than 20 minutes, the period of immersion of the product in the second bath being at least equal to the period of immersion in the first bath.
EP81200313A 1980-03-25 1981-03-20 Hot dip coating process Expired EP0037143B1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
BE6/47114A BE882430A (en) 1980-03-25 1980-03-25 HOT COATING PROCESS
BE47114 1980-03-25
BE47183 1980-06-09
BE47184 1980-06-09
BE6/47184A BE883725A (en) 1980-06-09 1980-06-09 PROTECTION METHOD BY MULTI-LAYERED MULTI-LAYER METAL COATINGS
BE6/47183A BE883724A (en) 1980-06-09 1980-06-09 PROCESS FOR HOT COATING OF SILICON STEELS

Publications (2)

Publication Number Publication Date
EP0037143A1 EP0037143A1 (en) 1981-10-07
EP0037143B1 true EP0037143B1 (en) 1985-03-20

Family

ID=27159690

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81200313A Expired EP0037143B1 (en) 1980-03-25 1981-03-20 Hot dip coating process

Country Status (2)

Country Link
EP (1) EP0037143B1 (en)
DE (1) DE3169319D1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10003680A1 (en) * 2000-01-28 2001-08-09 Thyssenkrupp Stahl Ag Method for producing a steel strip provided with a zinc coating and zinc coated steel strip

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0097487A3 (en) * 1982-06-17 1984-09-12 Uss Engineers And Consultants, Inc. Method of producing corrosion-resistant coatings on ferrous-base articles
US4401727A (en) * 1982-06-23 1983-08-30 Bethlehem Steel Corporation Ferrous product having an alloy coating thereon of Al-Zn-Mg-Si Alloy, and method
FR2548216B1 (en) * 1983-06-28 1988-10-21 Fical Fils Cables Acier Lens STEEL WIRE WITH CORROSION RESISTANT COATINGS
FR2554831B1 (en) * 1983-11-15 1993-08-13 Thomson Csf METHOD FOR DEPOSITING A PROTECTIVE COATING ON METAL PARTS
EP0148740A1 (en) * 1983-12-22 1985-07-17 CENTRE DE RECHERCHES METALLURGIQUES CENTRUM VOOR RESEARCH IN DE METALLURGIE Association sans but lucratif Method for hot coating and bath composition therefor
JPH01263255A (en) * 1988-04-14 1989-10-19 Nippon Aen Kogyo Kk Aluminum-zinc alloy hot dipping method with high coating weight
CA1335867C (en) * 1988-09-02 1995-06-13 Verdun Hildreth Farnsworth Rare earth and aluminium containing galvanising bath
CA2024210A1 (en) * 1989-11-06 1991-05-07 William D. Guenther Method of treating a ferrous component for subsequent metallurgical bonding to cast aluminum
SE510563C2 (en) * 1990-04-13 1999-06-07 Centre Rech Metallurgique Methods for continuous hot dip coating of a steel strip and steel strip coated with a Zn / Al alloy
JPH07109556A (en) * 1993-10-08 1995-04-25 Shinko Kosen Kogyo Kk Alloy layer coated steel wire and its production
JP4136286B2 (en) * 1999-08-09 2008-08-20 新日本製鐵株式会社 Zn-Al-Mg-Si alloy plated steel with excellent corrosion resistance and method for producing the same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB287201A (en) * 1926-11-19 1928-03-19 Evan Arthur Atkins Improvements in and connected with the galvanizing or coating by dipping of steel
GB337399A (en) * 1929-07-29 1930-10-29 American Rolling Mill Co Coated metal bodies and process of producing same
US3343930A (en) * 1964-07-14 1967-09-26 Bethlehem Steel Corp Ferrous metal article coated with an aluminum zinc alloy
US3393089A (en) * 1964-07-14 1968-07-16 Bethlehem Steel Corp Method of forming improved zinc-aluminum coating on ferrous surfaces
GB1121548A (en) * 1964-10-28 1968-07-31 Trefilerie Et Cablerie De Bour Improvements in or relating to the continuous heat treatment and "hot dipping" of metal wire and apparatus therefor
FR2027888A1 (en) * 1969-01-08 1970-10-02 Inland Steel Co Ferrous sheet galvanised with zinc alloy
FR2093906A1 (en) * 1970-09-25 1972-02-04 Lysaght Ltd John
DE2146376A1 (en) * 1970-09-17 1972-03-30 Fredericia Galvaniseringsansta Hot galvanising - iron and steel articles by immersion in zinc and then in zinc-aluminium alloys
US3952120A (en) * 1974-05-31 1976-04-20 Bethlehem Steel Corporation Aluminum-zinc coated low-alloy ferrous product and method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB876032A (en) * 1958-08-11 1961-08-30 British Non Ferrous Metals Res Improvements in or relating to the galvanizing of steel

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB287201A (en) * 1926-11-19 1928-03-19 Evan Arthur Atkins Improvements in and connected with the galvanizing or coating by dipping of steel
GB337399A (en) * 1929-07-29 1930-10-29 American Rolling Mill Co Coated metal bodies and process of producing same
US3343930A (en) * 1964-07-14 1967-09-26 Bethlehem Steel Corp Ferrous metal article coated with an aluminum zinc alloy
US3393089A (en) * 1964-07-14 1968-07-16 Bethlehem Steel Corp Method of forming improved zinc-aluminum coating on ferrous surfaces
GB1121548A (en) * 1964-10-28 1968-07-31 Trefilerie Et Cablerie De Bour Improvements in or relating to the continuous heat treatment and "hot dipping" of metal wire and apparatus therefor
FR2027888A1 (en) * 1969-01-08 1970-10-02 Inland Steel Co Ferrous sheet galvanised with zinc alloy
DE2146376A1 (en) * 1970-09-17 1972-03-30 Fredericia Galvaniseringsansta Hot galvanising - iron and steel articles by immersion in zinc and then in zinc-aluminium alloys
FR2093906A1 (en) * 1970-09-25 1972-02-04 Lysaght Ltd John
US3952120A (en) * 1974-05-31 1976-04-20 Bethlehem Steel Corporation Aluminum-zinc coated low-alloy ferrous product and method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10003680A1 (en) * 2000-01-28 2001-08-09 Thyssenkrupp Stahl Ag Method for producing a steel strip provided with a zinc coating and zinc coated steel strip
DE10003680C2 (en) * 2000-01-28 2003-04-10 Thyssenkrupp Stahl Ag Method for producing a steel strip provided with a zinc coating and zinc-coated steel strip

Also Published As

Publication number Publication date
EP0037143A1 (en) 1981-10-07
DE3169319D1 (en) 1985-04-25

Similar Documents

Publication Publication Date Title
RU2382833C2 (en) Method of coating on steel strip and steel strip (versions)
KR880000458B1 (en) Ferrous product having an alloy coating thereon of al-zn-mg-si alloy,and method
US5491036A (en) Coated strip
EP0037143B1 (en) Hot dip coating process
JP5270172B2 (en) Coated steel plate or strip
JPH05148668A (en) Aluminum-zinc-silicon alloy coating and its manufacture
JP2000328216A (en) High corrosion resistance plated steel sheet
KR850001323B1 (en) An aluminium-zinc alloy coated ferrous products to improve corrosion resistance
LU85453A1 (en) HOT GALVANIZED STEEL PRODUCT, IN PARTICULAR FOR USE AS A PHOSPHATE, AND PROCESS FOR PREPARING THE SAME
EP0594520B1 (en) Galvanized steel products and method of making
EP1029940B1 (en) Method of aluminizing steel for obtaining a thin interfacial layer
LU85886A1 (en) PROCESS FOR THE CONTINUOUS DEPOSITION OF A ZINC-ALUMINUM COATING ON A FERROUS PRODUCT, BY IMMERSION IN A MOLTEN METAL BATH
EP0710732B1 (en) Method for hot-dip coating without alloying a low interstitial steel plate
BE1011131A6 (en) Method of coating a steel strip by hot-dip galvanising
JPH0860329A (en) Production of galvannealed steel sheet
EP0042636A2 (en) Surface treatment of surfaces protected by a metallic coating
BE882430A (en) HOT COATING PROCESS
BE897788A (en) Zinc:aluminium:iron coating - made esp. by immersing substrate in molten zinc contg. aluminium and then using diffusion treatment
EP0111039A1 (en) Process for the high speed continuous galvanizing and annealing of a metallic wire
BE883724A (en) PROCESS FOR HOT COATING OF SILICON STEELS
JPH04214848A (en) Hot-dip galvanized coating material and method for hot-dip galvanizing
JPH0472047A (en) Aluminum/zinc alloy hot-dip coated material and aluminum/zinc alloy hot-dip coating method
BE1011425A3 (en) Method of coating a steel strip by hot-dip galvanising
EP0848076B1 (en) Method for hot-dip coating of a steel plate; galvanized or aluminized steel plate obtained therefrom
JPH04176852A (en) Aluminum-zinc alloy hot-dipping method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB IT LU

17P Request for examination filed

Effective date: 19820331

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CENTRE DE RECHERCHES METALLURGIQUES CENTRUM VOOR R

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB LU

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB LU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19850331

REF Corresponds to:

Ref document number: 3169319

Country of ref document: DE

Date of ref document: 19850425

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19860404

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19881118

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19881130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19881201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST