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EP1025275B2 - Method for making a composite metal product - Google Patents
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EP1025275B2 - Method for making a composite metal product - Google Patents

Method for making a composite metal product Download PDF

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Publication number
EP1025275B2
EP1025275B2 EP98948630A EP98948630A EP1025275B2 EP 1025275 B2 EP1025275 B2 EP 1025275B2 EP 98948630 A EP98948630 A EP 98948630A EP 98948630 A EP98948630 A EP 98948630A EP 1025275 B2 EP1025275 B2 EP 1025275B2
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EP
European Patent Office
Prior art keywords
strip
substance
vacuum chamber
temperature
diffusion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP98948630A
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German (de)
French (fr)
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EP1025275A1 (en
EP1025275B1 (en
Inventor
Pierre Van Den Brande
Alain Weymeersch
Fabrizio Maseri
Philippe Harlet
Lucien Renard
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ArcelorMittal Liege Upstream SA
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Cockerill Sambre SA
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Application filed by Cockerill Sambre SA filed Critical Cockerill Sambre SA
Priority to EP98948630A priority Critical patent/EP1025275B2/en
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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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals

Definitions

  • the present invention relates to a process for the composition of a metal product by the addition of at least one substance to this product.
  • composition of a steel is always isotropic since the setting composition is performed in the liquid phase of the metal. It is therefore impossible to make "composite” steels with ductile core and hard skin.
  • the proposed method according to the invention provides a solution to these various problems.
  • the composition of the steels after the solidification step makes it possible to work with standard compositions of very large volume at the steelworks, which makes it possible to eliminate the special castings and, consequently, to greatly reduce decommissioning problems. It is even possible to produce very small tonnages of special steels.
  • the supply of the aforementioned substance in the strip is carried out by the cathodic sputtering technique, by the vacuum evaporation technique, by arc deposition, by decomposition of a gas carrying this substance in a plasma or a combination of two or more of these techniques.
  • the invention relates to a method for modifying the chemical composition of a metal in the solid state in which a metal product in the form of a continuous strip is used. It moves to the parade in a vacuum chamber, in which there is for example a total gas pressure of 0.13 to 1 ⁇ 33 Pax10 4 Pa (10 -4 to 100 Torr) and in which one creates a plasma, next to a or both its faces, so as to introduce into said band, for example by bombardment and / or diffusion, a specific substance present in this chamber.
  • This band is heated and maintained at a sufficiently high temperature to allow at least the partial diffusion of this substance in the band. This temperature is, however, lower than the melting temperature of the material of which the strip is made.
  • the strip may, for example, be a mild steel strip, stainless steel or aluminum.
  • the strip is preferably maintained at a temperature of the order of 600 to 1200 ° C., whereas if it is aluminum, this temperature is generally of the order of 200 ° to 600 ° C.
  • the strip is advantageously preheated and the aforementioned substance is incorporated after an annealing step by means of discharges formed by plasma.
  • the attached figure shows an annealing installation in which the composition according to the invention can be made of a metal strip, which is preferably made of a steel sheet, moving in a substantially continuous manner through a vacuum chamber 2 of this installation in which the annealing is carried out by means of plasma discharges.
  • the discharges are established between the sheet 1, during its passage through a first zone 10 of this chamber 2, and a counterelectrode 3, in such a way as to dissipate the electric power from the discharges in this sheet 1 and thus therefore to create annealing.
  • the plasma can be created in direct current, the sheet then forming the cathode, or alternating current.
  • a counter-electrode 3 extending in the vacuum chamber or annealing chamber 2, opposite the sheet 1, and having a surface directed towards the sheet, the area of which is greater than that of the part of the sheet facing it, in order to maintain a negative self-bias of the latter.
  • the discharge may optionally be carried out in the presence of magnetic induction fields by virtue of the presence of magnets 5 near the sheet 1 and the opposite side thereof with respect to the counter electrode 3.
  • the power densities dissipated per face on the steel sheet 1 are typically between 1 W / cm 2 and 500 W / cm 2 , while the running speeds of this sheet are generally between 1 m / min and 1500 m / min.
  • the rise in temperature takes place in the area of the sheet where the power dissipation takes place, while the rate of rise in temperature depends on the adaptation of the power density used, the line speed as well as the thickness of the sheet and its heat capacity.
  • a temperature stabilization plateau in the annealing cycle can, for example, be obtained by providing in the vacuum chamber 2 an area where the sheet moves freely under reduced pressure. It is sufficient, for example, in such a case, to provide a compartment 6, somewhat isolated from the zone 10, where the heating takes place by the creation of the plasma. In this respect, it should be noted that, at reduced pressure, the heat losses by conduction in the gas are limited and the radiation losses can be restored to the sheet by means of reflectors or by radiant supplementary heating means. , not shown.
  • the supply of the above-mentioned substance can be obtained in zone 10 by any vacuum deposition system indicated schematically by reference 8, such as by sputtering by ions coming from a non-represented target or evaporation under vacuum, by arc deposition, or more generally by any technique of PVD ("physical vapor deposition") or by PECVD ("plasma enhanced chemical vapor deposition”). that is, by decomposition of a carrier gas of the substance in question, which is, for example, injected into the plasma, as shown schematically by the arrows 9 in the figure.
  • any vacuum deposition system indicated schematically by reference 8 such as by sputtering by ions coming from a non-represented target or evaporation under vacuum, by arc deposition, or more generally by any technique of PVD ("physical vapor deposition") or by PECVD ("plasma enhanced chemical vapor deposition”).
  • PVD physical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • the injection of the substance can be carried out in the holding zone 6 of the temperature in which a discharge can optionally be created.
  • the method according to the invention generally comprises a temperature rise step obtained by the heat losses of the plasma 4 produced at the strip 1, a temperature holding step in the compartment 6 where the band 1 is arranged accordion.
  • Example 1 Setting composition of a support for tinplate.
  • the basic steel has the following composition: C: 0.035%; N: 0.0025%; Ti: 0%; Mn: 0.4%; B: 0%; Al: 0.04%.
  • the band width is 1000 mm and its thickness is 0.2 mm.
  • the inlet temperature of the heating zone 10 is 20 ° C and that of entry from the zone 10 in the holding zone 6 is 800 ° C.
  • the rise in temperature is achieved by a plasma over a length of sheet of 7 m with a power consumption of 10 MW.
  • a reaction mixture consisting of 90% nitrogen and 10% C 2 H 2 is injected into the discharge.
  • the decomposed gas is then driven to the temperature holding zone 6.
  • the total gas pressure is 0.02 Torr. After this step, constituting a reactive annealing, the sheet is cooled and tinned.
  • the final carbon and nitrogen final composition of the thus cooled sheet is 0.06%.
  • Example 2 Setting composition of a boron steel.
  • This strip continuously enters the installation at a line speed of 200 m / min.
  • the bandwidth is 1000 mm.
  • the heating takes place over a strip length of 10 m and the power applied is 10 MW, so as to reach 800 ° C before entering the compartment 6.
  • a boron deposit is made on the surface of the sheet beforehand at annealing by vacuum evaporation at a rate of 0.04 g / m 2 of boron per side.
  • the temperature holding zone corresponds to 200 m of length of the sheet.
  • the final boron composition of the sheet at the outlet of the installation is 0.001% and that of the other elements has remained unchanged.

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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)
  • Physical Vapour Deposition (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)

Abstract

Adjusting the composition of a metal product by addition of at least one substance makes use of a metal product in the form of a continuous strip (1) being displaced in a vacuum chamber (2) with the substance being applied to the strip and being made to diffuse at least partially into the strip at the moment that it passes into the vacuum chamber by being maintained at a temperature lower than its fusion temperature, but sufficiently elevated to allow the diffusion.

Description

La présente invention est relative à un procédé pour la mise à composition d'un produit métallique par l'addition d'au moins une substance à ce produit.The present invention relates to a process for the composition of a metal product by the addition of at least one substance to this product.

Dans l'état actuel de la technologie sidérurgique, la mise à composition d'un acier au moyen d'une ou de plusieurs substances, est généralement réalisée en poche à l'aciérie, ce qui présente plusieurs inconvénients.In the current state of steel technology, the setting composition of a steel with one or more substances, is generally carried out in pocket at the steel mill, which has several disadvantages.

En effet, les volumes traités sont très importants, ce qui conduit à un certain manque de souplesse dans la mesure où certains produits nécessitent des coulées spéciales. Ceci est par exemple le cas pour des aciers au phosphore. Ces volumes conduisent aussi à des problèmes de flux souvent liés à des problèmes de déclassement des aciers.Indeed, the volumes treated are very important, which leads to a certain lack of flexibility in that some products require special castings. This is for example the case for phosphorus steels. These volumes also lead to flow problems often related to steel decommissioning problems.

Par ailleurs, la composition d'un acier est toujours isotrope puisque la mise à composition est réalisée dans la phase liquide du métal. Il est donc impossible de réaliser des aciers "composites" à coeur ductile et peau dure.Furthermore, the composition of a steel is always isotropic since the setting composition is performed in the liquid phase of the metal. It is therefore impossible to make "composite" steels with ductile core and hard skin.

De plus, la cristallisation et le développement de textures donnant lieu aux propriétés mécaniques optimales, telles que haute limite élastique, allongement élevé et emboutissabilité, est souvent difficile en présence de certains éléments, comme par exemple le carbone et le titane, qui pourraient être avantageusement introduits après l'étape de solidification du métal.In addition, the crystallization and development of textures giving rise to optimal mechanical properties, such as high yield strength, high elongation and drawability, is often difficult in the presence of certain elements, such as carbon and titanium, which could be advantageously introduced after the step of solidification of the metal.

Le procédé proposé suivant l'invention apporte une solution à ces différents problèmes.The proposed method according to the invention provides a solution to these various problems.

Grâce au procédé suivant l'invention, la mise à composition des aciers après l'étape de solidification permet de travailler avec des compositions standards de très grand volume à l'aciérie, ce qui permet d'éliminer les coulées spéciales et, par conséquent, de diminuer fortement les problèmes de déclassement. Il est même possible de produire de très faibles tonnages d'aciers spéciaux.By means of the process according to the invention, the composition of the steels after the solidification step makes it possible to work with standard compositions of very large volume at the steelworks, which makes it possible to eliminate the special castings and, consequently, to greatly reduce decommissioning problems. It is even possible to produce very small tonnages of special steels.

Il permet, en outre, de produire des aciers "composites" à gradient de composition entre la surface et le coeur. Il est ainsi, par exemple, possible de produire des aciers à peau dure et à coeur ductile.It also makes it possible to produce "composite" steels with a composition gradient between the surface and the core. It is thus possible, for example, to produce steels with hard skin and ductile core.

Suivant l'invention, on propose un procédé selon la revendication 1 qui permet la mise à composition d'aciers ou d'autres métaux après solidification. Ainsi, la cristallisation d'un acier à très faible teneur en carbone suivie de sa mise à composition est possible. Cette manière de procéder permet une amélioration des propriétés mécaniques par rapport au cas où la cristallisation est obtenue à composition finale.According to the invention, there is provided a process according to claim 1 which allows the composition of steels or other metals to be set after solidification. Thus, the crystallization of a very low carbon steel followed by its composition is possible. This way of proceeding allows an improvement of the mechanical properties with respect to the case where the crystallization is obtained with final composition.

On connaît un procédé pour la mise en composition d'un produit métallique se présentant sous la forme d'une bande continue par addition d'au moins une substance à ce produit, comprenant

  • un déplacement de la bande continue dans une chambre sous vide,
  • une application de la substance sur cette bande dans la chambre sous vide, et
  • une diffusion de ladite substance au moins partiellement dans la bande, en la maintenant à une température inférieure à la température de fusion, mais suffisamment élevée pour permettre cette diffusion
(voir par exemple JP-A-08158038 ).A process is known for the composition of a metallic product in the form of a continuous strip by adding at least one substance to this product, comprising
  • a displacement of the continuous strip in a vacuum chamber,
  • an application of the substance on this tape into the vacuum chamber, and
  • a diffusion of said substance at least partially in the band, maintaining it at a temperature below the melting temperature, but high enough to allow this diffusion
(see for example JP-A-08158038 ).

Pour résoudre les problèmes indiqués précédemment, on a prévu, suivant l'invention, un procédé de ce type, comprenant en outre

  • une étape de recuit au plasma qui a lieu dans la chambre sous vide, avec montée en température de la bande résultant d'une dissipation de puissance à partir dudit plasma, et ensuite
  • une étape de maintien en température dans la chambre sous vide, dans laquelle a lieu une incorporation de la substance précitée dans la bande métallique par ladite diffusion, après ladite étape de recuit.
In order to solve the problems indicated above, it has been provided, according to the invention, a method of this type, further comprising
  • a plasma annealing step which takes place in the vacuum chamber, with the temperature rise of the strip resulting from dissipation of power from said plasma, and then
  • a temperature maintenance step in the vacuum chamber, in which takes place an incorporation of the aforementioned substance in the metal strip by said diffusion, after said annealing step.

Suivant une forme de réalisation particulièrement avantageuse de l'invention, l'apport de la substance précitée dans la bande est réalisé par la technique de pulvérisation cathodique, par la technique d'évaporation sous vide, par dépôt par arc, par décomposition d'un gaz porteur de cette substance dans un plasma ou par une combinaison de deux ou plusieurs de ces techniques.According to a particularly advantageous embodiment of the invention, the supply of the aforementioned substance in the strip is carried out by the cathodic sputtering technique, by the vacuum evaporation technique, by arc deposition, by decomposition of a gas carrying this substance in a plasma or a combination of two or more of these techniques.

D'autres détails et particularités de l'invention ressortiront de la description donnée ci-après, à titre d'exemple non limitatif, de quelques formes de réalisation particulières de l'invention avec référence à la figure annexée, qui est une représentation schématique d'une installation pour la mise en oeuvre du procédé suivant l'invention. Dans cette description, les chiffres de référence se rapportent à cette figure.Other details and particularities of the invention will emerge from the description given below, by way of nonlimiting example, of some particular embodiments of the invention with reference to the appended figure, which is a diagrammatic representation of the invention. an installation for carrying out the process according to the invention. In this description, reference numerals refer to this figure.

D'une façon générale, l'invention concerne un procédé permettant la modification de la composition chimique d'un métal à l'état solide suivant lequel on fait usage d'un produit métallique se présentant sous forme d'une bande continue que l'on déplace au défilé dans une chambre sous vide, dans laquelle règne par exemple une pression totale de gaz de 0.13 à 1·33 Pax104Pa (10-4 à 100 Torr) et dans laquelle on crée un plasma, en regard d'une ou de ses deux faces, de manière à introduire dans ladite bande, par exemple par bombardement et/ou diffusion, une substance déterminée, présente dans cette chambre. Cette bande est chauffée et maintenue à une température suffisamment élevée pour permettre au moins la diffusion partielle de cette substance dans la bande. Cette température est, toutefois, inférieure à la température de fusion de la matière dont est constituée la bande. Il peut, par exemple, s'agir d'une bande en acier doux, en acier inoxydable ou en aluminium. Ainsi, dans le cas d'acier doux ou d'acier inoxydable, la bande est maintenue de préférence à une température de l'ordre de 600 à 1200°C, tandis que s'il s'agit d'aluminium, cette température est généralement de l'ordre de 200° à 600°C.In general, the invention relates to a method for modifying the chemical composition of a metal in the solid state in which a metal product in the form of a continuous strip is used. it moves to the parade in a vacuum chamber, in which there is for example a total gas pressure of 0.13 to 1 · 33 Pax10 4 Pa (10 -4 to 100 Torr) and in which one creates a plasma, next to a or both its faces, so as to introduce into said band, for example by bombardment and / or diffusion, a specific substance present in this chamber. This band is heated and maintained at a sufficiently high temperature to allow at least the partial diffusion of this substance in the band. This temperature is, however, lower than the melting temperature of the material of which the strip is made. It may, for example, be a mild steel strip, stainless steel or aluminum. Thus, in the case of mild steel or stainless steel, the strip is preferably maintained at a temperature of the order of 600 to 1200 ° C., whereas if it is aluminum, this temperature is generally of the order of 200 ° to 600 ° C.

Suivant l'invention, il faut en fait maintenir dans la chambre sous vide des conditions telles à permettre la diffusion de cette substance à partir de la surface de la bande vers le coeur de cette dernière et ainsi la mise à composition de celle-ci.According to the invention, it is necessary in fact to maintain in the vacuum chamber conditions such as to allow the diffusion of this substance from the surface of the strip towards the heart of the latter and thus the composition of the latter.

Pour permettre cette diffusion, on préchauffe avantageusement la bande et l'on incorpore la substance précitée après une étape de recuit au moyen de décharges formées par plasma.To allow this diffusion, the strip is advantageously preheated and the aforementioned substance is incorporated after an annealing step by means of discharges formed by plasma.

La figure annexée représente une installation de recuit dans laquelle peut être réalisée la mise à composition suivant l'invention d'une bande métallique, qui est de préférence constituée d'une tôle d'acier, se déplaçant d'une manière sensiblement continue à travers une chambre sous vide 2 de cette installation dans laquelle on réalise le recuit au moyen de décharges par plasma.The attached figure shows an annealing installation in which the composition according to the invention can be made of a metal strip, which is preferably made of a steel sheet, moving in a substantially continuous manner through a vacuum chamber 2 of this installation in which the annealing is carried out by means of plasma discharges.

Les décharges sont établies entre la tôle 1, lors de son passage à travers une première zone 10 de cette chambre 2, et une contre-électrode 3, d'une manière telle à dissiper la puissance électrique provenant des décharges dans cette tôle 1 et ainsi donc à créer le recuit.The discharges are established between the sheet 1, during its passage through a first zone 10 of this chamber 2, and a counterelectrode 3, in such a way as to dissipate the electric power from the discharges in this sheet 1 and thus therefore to create annealing.

Il s'agit, en fait, plus concrètement d'un procédé au cours duquel la tôle est bombardée par des ions en provenance d'un plasma 4 permettant un chauffage rapide et uniforme et, en même temps, un décapage de la surface de celle-ci.It is, in fact, more concretely a process in which the sheet is bombarded by ions from a plasma 4 allowing rapid and uniform heating and, at the same time, stripping the surface of that -this.

Le plasma peut être créé en courant continu, la tôle formant alors la cathode, ou en courant alternatif.The plasma can be created in direct current, the sheet then forming the cathode, or alternating current.

Dans ce dernier cas, on fait usage d'une contre-électrode 3 s'étendant dans la chambre sous vide ou de recuit 2, en regard de la tôle 1, et présentant une surface dirigée vers la tôle, dont la superficie est supérieure à celle de la partie de la tôle lui faisant face, afin de maintenir une auto-polarisation négative de cette dernière.In the latter case, use is made of a counter-electrode 3 extending in the vacuum chamber or annealing chamber 2, opposite the sheet 1, and having a surface directed towards the sheet, the area of which is greater than that of the part of the sheet facing it, in order to maintain a negative self-bias of the latter.

Comme dans le procédé classique de pulvérisation cathodique magnétron, la décharge peut éventuellement être réalisée en présence de champs d'induction magnétiques grâce à la présence d'aimants 5 à proximité de la tôle 1 et du côté opposé de celle-ci par rapport à la contre-électrode 3.As in the conventional magnetron sputtering method, the discharge may optionally be carried out in the presence of magnetic induction fields by virtue of the presence of magnets 5 near the sheet 1 and the opposite side thereof with respect to the counter electrode 3.

Les densités de puissance dissipées par face sur la tôle d'acier 1 sont typiquement comprises entre 1 W/cm2 et 500 W/cm2, alors que les vitesses de défilement de cette tôle sont généralement comprises entre 1 m/min et 1500 m/min.The power densities dissipated per face on the steel sheet 1 are typically between 1 W / cm 2 and 500 W / cm 2 , while the running speeds of this sheet are generally between 1 m / min and 1500 m / min.

La montée en température a lieu dans la zone de la tôle où se fait la dissipation de puissance, tandis que la vitesse de montée en température dépend de l'adaptation de la densité de puissance utilisée, de la vitesse de ligne ainsi que de l'épaisseur de la tôle et de sa capacité calorifique.The rise in temperature takes place in the area of the sheet where the power dissipation takes place, while the rate of rise in temperature depends on the adaptation of the power density used, the line speed as well as the thickness of the sheet and its heat capacity.

Dans certains cas, il peut être utile d'introduire un palier de stabilisation en température dans le cycle de recuit. Ceci peut, par exemple, être obtenu en prévoyant dans la chambre sous vide 2 une zone où la tôle défile librement sous une pression réduite. Il suffit, par exemple, dans un tel cas, de prévoir un compartiment 6, quelque peu isolé de la zone 10, où a lieu le réchauffement par la création du plasma. A cet égard, il y a lieu de noter qu'à pression réduite les pertes thermiques par conduction dans le gaz sont limitées et les pertes par radiation peuvent être restituées à la tôle au moyen de réflecteurs ou par des moyens de chauffage d'appoint radiants, non représentés.In some cases it may be useful to introduce a temperature stabilization plateau in the annealing cycle. This can, for example, be obtained by providing in the vacuum chamber 2 an area where the sheet moves freely under reduced pressure. It is sufficient, for example, in such a case, to provide a compartment 6, somewhat isolated from the zone 10, where the heating takes place by the creation of the plasma. In this respect, it should be noted that, at reduced pressure, the heat losses by conduction in the gas are limited and the radiation losses can be restored to the sheet by means of reflectors or by radiant supplementary heating means. , not shown.

Dans d'autres cas encore, il peut être utile de refroidir la tôle 1 dans la chambre sous vide 2, donc sous pression réduite, par exemple en faisant passer la tôle sur des cylindres de refroidissement 7.In still other cases, it may be useful to cool the sheet 1 in the vacuum chamber 2, thus under reduced pressure, for example by passing the sheet over cooling rolls 7.

Suivant l'invention, l'apport de la substance précitée peut être obtenu dans la zone 10 par n'importe quel système de dépôt sous vide indiqué schématiquement par la référence 8, tel que par pulvérisation cathodique (sputtering) par des ions en provenance d'une cible non représentée ou évaporation sous vide, par dépôt par arc, ou plus généralement par une technique quelconque de dépôt PVD ("physical vapor deposition"),ou encore par PECVD ("plasma enhanced chemical vapor deposition") c'est-à-dire par décomposition d'un gaz porteur de la substance en question, qui est, par exemple, injecté dans le plasma, comme montré schématiquement par les flèches 9 sur la figure.According to the invention, the supply of the above-mentioned substance can be obtained in zone 10 by any vacuum deposition system indicated schematically by reference 8, such as by sputtering by ions coming from a non-represented target or evaporation under vacuum, by arc deposition, or more generally by any technique of PVD ("physical vapor deposition") or by PECVD ("plasma enhanced chemical vapor deposition"). that is, by decomposition of a carrier gas of the substance in question, which is, for example, injected into the plasma, as shown schematically by the arrows 9 in the figure.

Dans une autre configuration de l'invention, l'injection de la substance peut être réalisée dans la zone de maintien 6 de la température dans laquelle on peut éventuellement créer une décharge.In another configuration of the invention, the injection of the substance can be carried out in the holding zone 6 of the temperature in which a discharge can optionally be created.

Comme il résulte déjà de ce qui précède, le procédé suivant l'invention comprend en général une étape de montée de température obtenue par les pertes thermiques du plasma 4 réalisé à la bande 1, une étape de maintien à température dans le compartiment 6 où la bande 1 est disposée en accordéon.As is already apparent from the foregoing, the method according to the invention generally comprises a temperature rise step obtained by the heat losses of the plasma 4 produced at the strip 1, a temperature holding step in the compartment 6 where the band 1 is arranged accordion.

Il s'est avéré, suivant l'invention, que c'est dans cette zone d'accumulation ou compartiment 6 qu'a lieu la diffusion de la substance, formant le ou les éléments d'addition à la composition de la bande, qui s'est fixée sur la surface de cette dernière, à partir de cette surface vers le coeur ou noyau de la bande. Ceci explique donc la possibilité de formation d'une bande métallique 1 à peau dure et à coeur ductile.It has been found, according to the invention, that it is in this accumulation zone or compartment 6 that the diffusion of the substance, forming the addition element or elements to the composition of the strip, takes place. has settled on the surface of the latter, from this surface to the core or core of the band. This therefore explains the possibility of forming a metal strip 1 with hard skin and ductile core.

Il est, toutefois, également possible d'obtenir une bande métallique dans laquelle la substance ou l'élément d'addition se répartit d'une manière homogène à travers toute son épaisseur. Il suffit d'adapter la température et le temps de maintien de cette température dans le compartiment 6.It is, however, also possible to obtain a metal strip in which the substance or the additive element is distributed homogeneously throughout its thickness. It suffices to adapt the temperature and the holding time of this temperature in compartment 6.

Par ailleurs, il est également possible de revêtir la bande dans la compartiment 6 ou dans un compartiment particulier subséquent avant le refroidissement de la bande par un film de finition ou de protection par des techniques connues en soi.Furthermore, it is also possible to coat the strip in the compartment 6 or in a particular compartment after the cooling of the band by a finishing film or protection by techniques known per se.

Ci-après, sont donnés deux exemples pratiques permettant d'illustrer davantage le procédé suivant l'invention appliqué dans une installation du type de celle représentée à la figure annexée.Hereinafter are given two practical examples to further illustrate the process according to the invention applied in an installation of the type shown in the attached figure.

Exemple 1 : Mise à composition d'un support pour fer blanc. Example 1 : Setting composition of a support for tinplate.

Il s'agit plus particulièrement de la mise à composition en carbone et en azote d'une tôle d'acier destinée à être étamée. L'acier de base a la composition suivante :
C : 0,035 % ; N : 0,0025 % ; Ti : 0 % ; Mn : 0,4 % ; B : 0 % ; Al : 0,04 %.It is more particularly the setting composition carbon and nitrogen of a steel sheet to be tinned. The basic steel has the following composition:
C: 0.035%; N: 0.0025%; Ti: 0%; Mn: 0.4%; B: 0%; Al: 0.04%.

L'acier entre en continu dans l'installation à une vitesse de ligne de 600 m/min. La largeur de bande est de 1000 mm et son épaisseur est de 0,2 mm. La température d'entrée de la zone de chauffe 10 est de 20°C et celle d'entrée à partir de la zone 10 dans la zone de maintien 6 est de 800°C. La montée en température est réalisée par un plasma sur une longueur de tôle de 7 m avec une puissance consommée de 10 MW. On injecte un mélange réactif constitué de 90 % d'azote et de 10 % de C2H2 dans la décharge. Le gaz décomposé est alors entraîné vers la zone de maintien en température 6. La pression totale de gaz est de 0,02 Torr. Après cette étape, constituant en fait un recuit réactif, la tôle est refroidie et étamée. La composition finale moyenne en carbone et en azote de la tôle ainsi refroidie est de 0,06 %.Steel enters the plant continuously at a line speed of 600 m / min. The band width is 1000 mm and its thickness is 0.2 mm. The inlet temperature of the heating zone 10 is 20 ° C and that of entry from the zone 10 in the holding zone 6 is 800 ° C. The rise in temperature is achieved by a plasma over a length of sheet of 7 m with a power consumption of 10 MW. A reaction mixture consisting of 90% nitrogen and 10% C 2 H 2 is injected into the discharge. The decomposed gas is then driven to the temperature holding zone 6. The total gas pressure is 0.02 Torr. After this step, constituting a reactive annealing, the sheet is cooled and tinned. The final carbon and nitrogen final composition of the thus cooled sheet is 0.06%.

Exemple 2 : Mise à composition d'un acier au bore. Example 2 : Setting composition of a boron steel.

On fait usage d'une tôle en un acier ULCTi ("Ultra Low Carbone Ti") de 1 mm d'épaisseur, dont la composition est la suivante :
C : 0,003%; N: 0,0025%; Ti: 0,06%; Mn:0,15%; B:0%; Al : 0,04 %.It uses a sheet of a steel ULCTi ("Ultra Low Carbon Ti") 1 mm thick, whose composition is as follows:
C: 0.003%; N: 0.0025%; Ti: 0.06%; Mn: 0.15%; B: 0%; Al: 0.04%.

Cette bande entre en continu dans l'installation à une vitesse de ligne de 200 m/min. La largeur de bande est de 1000 mm.This strip continuously enters the installation at a line speed of 200 m / min. The bandwidth is 1000 mm.

Le chauffage a lieu sur une longueur de bande de 10 m et la puissance appliquée est de 10 MW, de manière à atteindre 800°C avant d'entrer dans le compartiment 6. Un dépôt du bore est réalisé sur la surface de la tôle préalablement au recuit par évaporation sous vide à raison de 0,04 g/m2 de bore par face.The heating takes place over a strip length of 10 m and the power applied is 10 MW, so as to reach 800 ° C before entering the compartment 6. A boron deposit is made on the surface of the sheet beforehand at annealing by vacuum evaporation at a rate of 0.04 g / m 2 of boron per side.

La zone de maintien à température correspond à 200 m de longueur de la tôle.The temperature holding zone corresponds to 200 m of length of the sheet.

La composition finale en bore de la tôle à la sortie de l'installation est de 0,001 % et celle des autres éléments est restée inchangée.The final boron composition of the sheet at the outlet of the installation is 0.001% and that of the other elements has remained unchanged.

Il est bien entendu que l'invention n'est pas limitée aux formes de réalisation décrites ci-dessus, mais que de nombreuses variantes peuvent être envisagées sans sortir du cadre de la présente invention telle que définie dans les revendications, notamment en ce qui concerne les conditions de recuit et de diffusion d'une substance d'addition destinée à la mise à composition de la bande métallique.It is understood that the invention is not limited to the embodiments described above, but that many variants can be envisaged without departing from the scope of the present invention as defined in the claims, especially with regard to the conditions of annealing and diffusion of an addition substance for the composition of the metal strip.

Claims (4)

  1. Method for making a composite metal product in the form of a continuous strip by adding at least one substance to this product, comprising
    - movement of the continuous strip in a vacuum chamber,
    - application of the substance to this strip in the vacuum chamber, and
    - diffusion of the said substance at least partially in the strip, while maintaining it at a temperature below its melting point, but sufficiently high to enable this diffusion to take place,
    characterised in that it also comprises
    a step of plasma annealing that takes place in the vacuum chamber, with a rise in temperature of the strip resulting from a dissipation of power from the said plasma, and then
    a temperature maintenance step in the vacuum chamber, in which an incorporation of the aforementioned substance takes place in the metal strip by the said diffusion, after the said plasma annealing step.
  2. Method according to claim 1, characterised in that the substance is put in contact with the strip when it is maintained at a sufficiently high temperature to enable the substance to be at least partially diffused in the strip.
  3. Method according to one or other of claims 1 and 2, characterised in that the aforementioned substance is added in the strip (1) by the technique of cathodic sputtering, vacuum evaporation, arc deposition or more generally by a technique of decomposition of a gas carrying this substance or by a combination of two or more of the aforementioned techniques.
  4. Method according to any one of claims 1 to 3, characterised in that a strip (1) of soft steel, stainless steel or aluminium is used.
EP98948630A 1997-10-17 1998-10-16 Method for making a composite metal product Expired - Lifetime EP1025275B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98948630A EP1025275B2 (en) 1997-10-17 1998-10-16 Method for making a composite metal product

Applications Claiming Priority (4)

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EP97203241A EP0909832A1 (en) 1997-10-17 1997-10-17 Process for adjusting the composition of a metallic product
EP97203241 1997-10-17
PCT/BE1998/000154 WO1999020808A1 (en) 1997-10-17 1998-10-16 Method for making a composite metal product
EP98948630A EP1025275B2 (en) 1997-10-17 1998-10-16 Method for making a composite metal product

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EP1025275A1 EP1025275A1 (en) 2000-08-09
EP1025275B1 EP1025275B1 (en) 2003-11-05
EP1025275B2 true EP1025275B2 (en) 2010-12-15

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EP (2) EP0909832A1 (en)
JP (1) JP4050461B2 (en)
AT (1) ATE253650T1 (en)
AU (1) AU9524898A (en)
DE (1) DE69819552T3 (en)
DK (1) DK1025275T4 (en)
ES (1) ES2210827T5 (en)
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WO (1) WO1999020808A1 (en)

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EP2307581A1 (en) * 2008-06-30 2011-04-13 Eaton Corporation Continuous production system for magnetic processing of metals and alloys to tailor next generation materials
JP5942884B2 (en) 2013-02-18 2016-06-29 Ｊｆｅスチール株式会社 Nitriding equipment and nitriding method for grain-oriented electrical steel sheet
JP5942886B2 (en) * 2013-02-18 2016-06-29 Ｊｆｅスチール株式会社 Nitriding equipment and nitriding method for grain-oriented electrical steel sheet

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804679A (en) † 1968-05-21 1974-04-16 Cockerill Method of coating steel products
DE1925497C3 (en) † 1968-05-21 1974-04-18 Centre De Recherches Metallurgiques T-Centrum Voor Research In De Metallurgie, Bruessel Process for the production of metallic layers on workpieces made of steel
EP0181830A2 (en) † 1984-11-08 1986-05-21 Mitsubishi Jukogyo Kabushiki Kaisha Method and apparatus for heating a strip of metallic material in a continuous annealing furnace
US5062900A (en) † 1988-04-18 1991-11-05 Institut De Recherches De La Siderurgie Francaise Process for the improvement of the corrosion resistance of metallic materials
FR2704239A1 (en) † 1993-04-23 1994-10-28 Ugine Sa Process for enriching with an alloying element a sheet made of magnetic steel
JPH08158038A (en) † 1994-11-29 1996-06-18 Kawasaki Steel Corp Metal strip continuous plasma processing equipment
DE19527515C1 (en) † 1995-07-27 1996-11-28 Fraunhofer Ges Forschung Corrosion-resistant steel sheet prodn., e.g. for the automobile industry
EP0889311A1 (en) † 1997-07-04 1999-01-07 Sollac Tightness testing of radiant tubes in industrial furnaces

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS604265B2 (en) * 1980-05-30 1985-02-02 松下電器産業株式会社 Aluminum boronization method
US4872926A (en) * 1987-12-30 1989-10-10 American Air Liquide Process for heat treating metals or metal alloys in a thermal plasma
US5232789A (en) * 1989-03-09 1993-08-03 Mtu Motoren- Und Turbinen-Union Muenchen Gmbh Structural component with a protective coating having a nickel or cobalt basis and method for making such a coating
JPH03177560A (en) * 1989-12-06 1991-08-01 Nippon Steel Corp Production of sheet-like material having electric insulating property
DE4211167A1 (en) * 1992-03-31 1993-10-07 Thaelmann Schwermaschbau Veb Method and device for the continuous thermal surface treatment of rod or strand-shaped materials with a metallic surface
US5431746A (en) * 1993-08-30 1995-07-11 Sps Technologies, Inc. Method for making thin magnetic strips
JP3177560B2 (en) 1994-03-31 2001-06-18 富士機工株式会社 Seat reclining device
BE1010913A3 (en) * 1997-02-11 1999-03-02 Cockerill Rech & Dev Annealing process substrate metal in parade.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804679A (en) † 1968-05-21 1974-04-16 Cockerill Method of coating steel products
DE1925497C3 (en) † 1968-05-21 1974-04-18 Centre De Recherches Metallurgiques T-Centrum Voor Research In De Metallurgie, Bruessel Process for the production of metallic layers on workpieces made of steel
EP0181830A2 (en) † 1984-11-08 1986-05-21 Mitsubishi Jukogyo Kabushiki Kaisha Method and apparatus for heating a strip of metallic material in a continuous annealing furnace
US5062900A (en) † 1988-04-18 1991-11-05 Institut De Recherches De La Siderurgie Francaise Process for the improvement of the corrosion resistance of metallic materials
FR2704239A1 (en) † 1993-04-23 1994-10-28 Ugine Sa Process for enriching with an alloying element a sheet made of magnetic steel
JPH08158038A (en) † 1994-11-29 1996-06-18 Kawasaki Steel Corp Metal strip continuous plasma processing equipment
DE19527515C1 (en) † 1995-07-27 1996-11-28 Fraunhofer Ges Forschung Corrosion-resistant steel sheet prodn., e.g. for the automobile industry
EP0756022A2 (en) † 1995-07-27 1997-01-29 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Steel sheet protected against corrosion and process for its production
EP0889311A1 (en) † 1997-07-04 1999-01-07 Sollac Tightness testing of radiant tubes in industrial furnaces

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DR.C METZNER ET AL: "Forschungsbericht 13N6139 im Forschungsschwerpunkt Oberflächen- und Schichttechnologien:"Entwicklung neuartiger, durch Hochrate-Elektronenstrahlbedampfung herstellbarer Schichtverbunde und deren Eigenschaften"", October 1996, BUNDESMINISTERIUM FÜR BILDUNG,WISSENSCHAFT, FORSCHUNG UND TECHNOLOGIE, article "pp 36-55 und 88-96", pages: 1 - 25 †
E.C.JONES: "Plasma Immersion Ion Implantation for Electronic materials", JPN J.APPL.PHYS., vol. 35, 1996, pages 1027 - 1036 †

Also Published As

Publication number Publication date
PT1025275E (en) 2004-03-31
DE69819552D1 (en) 2003-12-11
EP0909832A1 (en) 1999-04-21
EP1025275A1 (en) 2000-08-09
JP4050461B2 (en) 2008-02-20
AU9524898A (en) 1999-05-10
DK1025275T4 (en) 2011-03-21
ES2210827T5 (en) 2011-05-04
US6361628B1 (en) 2002-03-26
ATE253650T1 (en) 2003-11-15
EP1025275B1 (en) 2003-11-05
JP2001520319A (en) 2001-10-30
DE69819552T2 (en) 2004-05-13
ES2210827T3 (en) 2004-07-01
DE69819552T3 (en) 2011-06-09
WO1999020808A1 (en) 1999-04-29
DK1025275T3 (en) 2004-03-15

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