EP1858662A1 - Method for continuous casting of a metal with improved mechanical strength and product obtained by said method - Google Patents

Method for continuous casting of a metal with improved mechanical strength and product obtained by said method

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Publication number
EP1858662A1
EP1858662A1 EP06701517A EP06701517A EP1858662A1 EP 1858662 A1 EP1858662 A1 EP 1858662A1 EP 06701517 A EP06701517 A EP 06701517A EP 06701517 A EP06701517 A EP 06701517A EP 1858662 A1 EP1858662 A1 EP 1858662A1
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EP
European Patent Office
Prior art keywords
nozzle
metal
nanoparticles
jet
ceramic
Prior art date
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Granted
Application number
EP06701517A
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German (de)
French (fr)
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EP1858662B1 (en
Inventor
Paul Naveau
Astrid De Ro
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Centre de Recherches Metallurgiques CRM ASBL
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Centre de Recherches Metallurgiques CRM ASBL
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Publication of EP1858662A1 publication Critical patent/EP1858662A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/108—Feeding additives, powders, or the like

Definitions

  • the present invention relates to a new process for the continuous casting of a molten metal, in particular steel, to obtain an intermediate product such as slab, billet, wire, etc., before subsequent thermomechanical treatment such as rolling, continuous annealing, etc., so that its chemical composition has been modified by adding elements, in order to give it a higher mechanical strength.
  • the following description refers more particularly to the continuous casting of steel. This choice, however, is only an example and does not involve any limitation of the invention.
  • the invention also relates to the product with improved mechanical characteristics obtained by the method.
  • the technique of continuous casting of steel is well known. It essentially consists in supplying, with molten steel coming from a ladle or a tundish, a cooled copper or copper alloy mold, called a continuous casting mold, the latter being open. at its lower end, and to extract through this opening an ingot in the form of a continuous strand partially solidified.
  • the molten steel is introduced into the mold by means of at least one nozzle, that is to say a generally tubular element disposed between the tundish and the mold.
  • the lower end of the nozzle is usually provided with one or two outlets located in the axis of the nozzle or laterally, and opens under the free level of liquid steel present in the mold.
  • nozzles for obtaining a better cooling of the superheated liquid steel from the tundish.
  • the goal is to obtain pasty steel at the inlet of the mold.
  • These nozzles may in particular have a heat exchanger consisting of a water-cooled copper tube or a deflector or dome. It acts to force the superheated steel to flow in a thin layer along the walls of the nozzle, which significantly increases the heat exchange surface.
  • the cooling of the duct ensures the elimination of the overheating of the steel and causes the appearance of a solid fraction which makes the pasty steel at its inlet into the ingot mold.
  • a protective gas under pressure for example argon
  • the introduction of a protective gas under pressure, for example argon, in the conduit causes an overpressure which prevents any entrainment of air by the liquid steel, which would lead to the oxidation thereof or to the formation of alumina with plugging of the nozzle.
  • the technique described in patent EP-B-269 180 is called hollow jet casting or by means of a HJN nozzle for hollow jet nozzle.
  • a continuous casting nozzle having in its upper part a dome-shaped distributor device designed to separate the liquid steel in two jets, a internal jet and an external jet, in two physically separated areas.
  • Finely divided gaseous, liquid or solid material injecting means under the dome in the inner zone allow the formation of a steel of different chemical composition from that of the base steel, poured into the outer zone.
  • thermomechanical treatments to increase the mechanical characteristics of a steel for example by the microstructure (martensite, bainite, etc.) or endogenous precipitation, have the disadvantage that the structure of the steel finally obtained can be altered by a thermal after-treatment of the product (eg welding, galvanizing, etc.). It would therefore be desirable, at least in certain cases, to be able to directly cast a product whose structure and consequently the mechanical properties are stable throughout the subsequent treatments that the product could undergo.
  • the present invention aims to provide a solution that allows to overcome the disadvantages of the state of the art.
  • the present invention is aimed in particular at providing a continuous casting process which makes it possible to obtain slabs or billets of composition adapted to impart to the steel a greater mechanical strength before rolling.
  • the invention aims in particular to obtain a steel of homogeneous chemical composition and / or stabilized structure vis-à-vis a rolling process and / or thermomechanical treatment after casting.
  • a particular object of the present invention is to use the hollow jet technique to inject through the continuous casting nozzle finely divided ceramic particles.
  • a first object of the present invention relates to a method for the continuous casting of a metal in the form of a hollow jet in a nozzle located between a ladle or a tundish and a continuous casting mold, said nozzle comprising in its upper part a distributor member capable of deflecting at least a portion of the liquid metal arriving at the inlet of the nozzle towards an inner wall of the nozzle before it enters the ingot mold, said method comprising an injection into an interior volume of the hollow jet of finely divided solid material, characterized in that the finely divided solid material comprises technical ceramic nanoparticles, of characteristic size less than 200 nm and preferably 100 nm.
  • the technical ceramic nanoparticles comprise nanoparticles of oxides, nitrides, carbides, borides, silicides and / or compounds thereof.
  • the oxides are Al 2 O 3 , TiO 2 , SiO 2 , MgO, ZrO 2 or Y 2 O 3 .
  • the size of the nanoparticles is between 10 and 100 nm.
  • the amount of nanoparticles incorporated in the liquid metal is less than or equal to 5 percent, preferably between 0.1 and 1 percent, by weight of cast metal.
  • the ceramic nanoparticles injected into the interior volume of the hollow jet of the nozzle are suspended in a non-oxidizing gas, preferably argon, said gas being slight overpressure with respect to the atmospheric pressure and at most equal to the static pressure of the metal cast at the inlet thereof into the mold.
  • the ceramic nanoparticles are injected into the interior volume of the hollow jet of the nozzle by means of a mechanical transport device such as a worm.
  • the nanoparticles are agglomerated, prior to their injection into the nozzle, into microparticles of size essentially between 10 and 1000 microns, preferably between 100 and 200 microns.
  • the nanoparticles are agglomerated in a metal matrix or not of the same metal as the cast metal.
  • the cast metal is liquid steel and the metal matrix is an iron matrix or the metal matrix comprises an alloy metal other than iron.
  • the agglomeration of the nanoparticles is obtained by mixing nanoparticles of ceramic with micrometric particles of iron, that is to say of size greater than 10 microns, and preferably less than 20 microns.
  • said mixture is made by premixing in a slurry, followed by drying, milling, isostatic pressing and regrinding.
  • said mixture is made by a high energy hype of "mechanical alloying" type to obtain an insertion of ceramics in the iron matrix.
  • the hollow jet nozzle used is of the rotating jet type, that is to say composed of a vertical duct comprising in its upper part a dome-shaped distribution member, whose function is to divert the liquid metal entering the nozzle to the inner surface of said conduit and which has a plurality of arms symmetrically arranged in a star with respect to the axis of the nozzle and inclined relative to the horizontal, said arms being configured for printing on the liquid steel a helical twist movement along the inner wall of the nozzle.
  • the hollow jet nozzle used has in its upper part a dome-shaped distributor member designed to separate the liquid metal into two jets, an inner jet and an outer jet, in two physically good zones.
  • injection '• ceramic nanoparticles can be performed in the outer area of the nozzle.
  • a second subject of the present invention relates to a metal, preferably a steel, of high mechanical strength occurring after casting in the form of a continuous strand ingot at the outlet of a continuous casting mold, specially obtained by the method described above, and comprising less than one percent by weight of technical ceramic homogeneously distributed in at least a portion of the ingot.
  • the addition of particles in the liquid metal is carried out directly at the level of the continuous casting nozzle, since this, in the embodiments generally employed, and described above, generally comprises means for the introduction of alloying elements or oxides in at least a fraction of the liquid metal passing through the nozzle.
  • the added particles are ceramic particles. It is known to those skilled in the art that they are called technical ceramics or industrial class of manufactured materials that are non-metallic and inorganic. They are divided into two major families: oxides (for example Al 2 O 3 , TiCb,
  • the ceramic particles will have to meet the following operational definition: they are of nanometric size, typically 10-100 nanometers
  • the amounts of nanoparticles added to the liquid steel are 1 percent by weight.
  • the wettability of the particles in the liquid steel is the most important criterion for the choice of particles and the resolution of this technical problem is at the heart of the present invention.
  • a homogeneous distribution of the nanoparticles in the liquid steel is essential, which excludes a confinement of the powders injected on the surface of the liquid steel.
  • the particles may advantageously be agglomerated to a size of 100-200 ⁇ m to be injected through the nozzle HJN.
  • the nanoscale ceramic particles can be agglomerated in an iron matrix. or metal to obtain a compound whose characteristic final size is 100-200 ⁇ m.
  • the iron or metal matrix promotes the dispersion of the particles in the liquid steel.
  • nanometric particles of ceramic mixed with micrometric particles of iron (the size of which is for example 10 to 20 microns) are used.
  • the mixture is produced either by: - mixing in a slip, followed by drying, grinding, isostatic pressing and regrinding; high-energy hitting (mechanical alloying) to obtain an insertion of ceramics into the iron matrix. Threshing is an operation of bringing into contact and introducing an element into an assembly formed of one or more different elements of the first element by exerting a force on the element.

Abstract

The invention concerns a method for continuous casting of a metal in the form of a hollow jet into a nozzle arranged between a pouring ladle or a tundish and a continuous casting ingot mold, said nozzle including in its upper part a dispensing member capable of deflecting at least part of the liquid metal reaching the nozzle inlet towards an inner wall of the nozzle before it penetrates into the ingot mold. Said method includes injecting into an inner volume of the hollow jet finely-divided solid material, characterized in that the finely-divided solid material comprises technical ceramic nanoparticles, of characteristic size less than 200 nm and preferably less than 100 nm.

Description

PROCEDE POUR COULER EN CONTINU UN METAL A RESISTANCE MECANIQUE AMELIOREE ET PRODUIT OBTENU PAR LE PROCEDE PROCESS FOR CONTINUOUSLY CUTTING A METAL WITH IMPROVED MECHANICAL RESISTANCE AND PRODUCT OBTAINED BY THE PROCESS
Objet de l'inventionObject of the invention
[0001] La présente invention se rapporte à un nouveau procédé pour la coulée en continu d'un métal en fusion, en particulier de l'acier, permettant d'obtenir un produit intermédiaire tel que brame, billette, fil, etc., avant traitement thermomécanique ultérieur tel que laminage, recuit continu, etc., de sorte que sa composition chimique a été modifiée par ajout d'éléments, en vue de lui conférer une résistance mécanique plus élevée. [0002] La description qui suit fait plus particulièrement référence à la coulée continue de l'acier. Ce choix n'a toutefois qu'un caractère d'exemple et n'entraîne aucune limitation de l'invention. [0003] L'invention se rapporte également au produit à caractéristiques mécaniques améliorées obtenu par le procédé.The present invention relates to a new process for the continuous casting of a molten metal, in particular steel, to obtain an intermediate product such as slab, billet, wire, etc., before subsequent thermomechanical treatment such as rolling, continuous annealing, etc., so that its chemical composition has been modified by adding elements, in order to give it a higher mechanical strength. The following description refers more particularly to the continuous casting of steel. This choice, however, is only an example and does not involve any limitation of the invention. The invention also relates to the product with improved mechanical characteristics obtained by the method.
Etat de la techniqueState of the art
[0004] La technique de coulée continue d'acier est bien connue. Elle consiste essentiellement à alimenter, avec de l'acier en fusion provenant d'une poche de coulée ou d'un panier répartiteur (tundish) , un moule refroidi en cuivre ou alliage de cuivre, appelé lingotière de coulée continue, cette dernière étant ouverte à son extrémité inférieure, et à en extraire par cette ouverture un lingot sous forme d'un brin continu partiellement solidifié. [0005] En général, l'acier en fusion est introduit dans la lingotière au moyen d'au moins une busette, c'est- à-dire un élément généralement tubulaire disposé entre le panier répartiteur et la lingotière. L'extrémité inférieure de la busette est pourvue habituellement d'un ou deux orifices de sortie sis dans l'axe de la busette ou latéralement, et débouche sous le niveau libre d'acier liquide présent dans la lingotière. [0006] On connaît . également des évolutions des busettes destinées à obtenir un meilleur refroidissement de l'acier liquide surchauffé en provenance du panier répartiteur. Le but est d'obtenir de l'acier pâteux à l'entrée de la lingotière. Ces busettes peuvent présenter notamment un échangeur de chaleur constitué d'un tube en cuivre refroidi à eau ou encore un déflecteur ou dôme. Celui-ci a pour rôle de forcer l'acier surchauffé à ruisseler en une couche mince le long des parois de la busette, ce qui permet d'augmenter notablement la surface d'échange thermique. Le refroidissement du conduit assure l'élimination de la surchauffe de l'acier et provoque l'apparition d'une fraction solide qui rend l'acier pâteux à son entrée dans" la lingotière. L'introduction d'un gaz protecteur sous pression, par exemple de l'argon, dans le conduit provoque une surpression qui empêche tout entraînement d'air par l'acier liquide, qui conduirait à l'oxydation de celui-ci ou à la formation d'alumine avec bouchage de la busette. Cette technique décrite dans le brevet EP-B-269 180 porte le nom de coulée en jet creux ou au moyen d'une busette HJN pour hollow jet nozzle. [0007] Une autre évolution, décrite dans le brevet EP-B-605 37.9, se rapporte à l'injection dans le jet creux d'une certaine quantité de matière métallique finement divisée, en utilisant comme vecteur un gaz non oxydant en légère surpression par rapport à la pression atmosphérique, afin d'empêcher toute entrée d'air. Le but est d'obtenir, selon le cas, un affinement de la structure de solidification par création de nouveaux germes de solidification ou une modification de la composition chimique de base de l'acier.The technique of continuous casting of steel is well known. It essentially consists in supplying, with molten steel coming from a ladle or a tundish, a cooled copper or copper alloy mold, called a continuous casting mold, the latter being open. at its lower end, and to extract through this opening an ingot in the form of a continuous strand partially solidified. In general, the molten steel is introduced into the mold by means of at least one nozzle, that is to say a generally tubular element disposed between the tundish and the mold. The lower end of the nozzle is usually provided with one or two outlets located in the axis of the nozzle or laterally, and opens under the free level of liquid steel present in the mold. [0006] We know. also evolutions of the nozzles for obtaining a better cooling of the superheated liquid steel from the tundish. The goal is to obtain pasty steel at the inlet of the mold. These nozzles may in particular have a heat exchanger consisting of a water-cooled copper tube or a deflector or dome. It acts to force the superheated steel to flow in a thin layer along the walls of the nozzle, which significantly increases the heat exchange surface. The cooling of the duct ensures the elimination of the overheating of the steel and causes the appearance of a solid fraction which makes the pasty steel at its inlet into the ingot mold.The introduction of a protective gas under pressure, for example argon, in the conduit causes an overpressure which prevents any entrainment of air by the liquid steel, which would lead to the oxidation thereof or to the formation of alumina with plugging of the nozzle. The technique described in patent EP-B-269 180 is called hollow jet casting or by means of a HJN nozzle for hollow jet nozzle. [0007] Another development, described in patent EP-B-605 37.9, relates to the injection into the hollow jet of a certain quantity of finely divided metallic material, using as vector a non-oxidizing gas at a slight overpressure with respect to the atmospheric pressure, to prevent any entry of air. The aim is to obtain, as the case may be, a refinement of the solidification structure by creating new solidification nuclei or a modification of the basic chemical composition of the steel.
[0008] On connaît encore une busette de coulée continue à jet tournant, décrite dans le brevet BE-A-IOl 20 37, composée d'un conduit vertical comprenant dans sa partie supérieure un organe répartiteur ou dôme, dont la fonction est également de dévier le métal entrant dans la busette vers la surface intérieure dudit conduit et qui comporte trois bras disposés en étoile par rapport à l'axe de la busette et inclinés par rapport à l'horizontale. Ces bras sont configurés pour imprimer à 1 ' acier liquide un mouvement tournant hélicoïdal le long de la paroi interne. L'acier liquide sort alors par deux ouïes latérales de la busette avec une vitesse nettement plus faible que celle obtenue avec une busette conventionnelle pour un même débit, ce qui améliore la qualité des lingots extraits (moins d'inclusions et de bulles de gaz).[0008] There is also known a rotating casting nozzle, described in patent BE-A-101137, composed of a vertical duct comprising in its upper part a distributor or dome, the function of which is also diverting the metal entering the nozzle to the inner surface of said conduit and which has three arms arranged in a star with respect to the axis of the nozzle and inclined relative to the horizontal. These arms are configured to print to the liquid steel a helical twist movement along the inner wall. The liquid steel then leaves by two lateral openings of the nozzle with a much lower speed than that obtained with a conventional nozzle for the same flow, which improves the quality of the ingots extracted (fewer inclusions and gas bubbles) .
[0009] La coulée continue de produits à base d'acier de composition chimique mixte ou bi-composants a également suscité un très grand intérêt dans un nombre important d'applications spécifiques, aussi bien pour les produits longs que pour les produits plats (par exemple réduction de la teneur en silicium à la surface des brames, afin d'améliorer l'aptitude à la galvanisation des produits laminés ; modification de la teneur en carbone en surface des aciers péritectiques pour améliorer leur coulabilité ; coulée de produits dont les propriétés mécaniques varient le long de leur épaisseur, comme par exemple une haute résistance en surface et une grande ductilité à cœur, etc.). Le terme bi-cpmposants désigne des produits dont la composition chimique de l'acier est différente selon l'endroit du produit investigué, par exemple différente en peau par rapport au cœur. Pour répondre à ce besoin, la Demanderesse a proposé, dans la demande internationale WO- A-02/30598, une busette de coulée continue présentant dans sa partie supérieure un organe répartiteur à dôme conçu pour séparer l'acier liquide en deux jets, un jet interne et un jet externe, dans deux zones physiquement bien séparées. Des moyens d'injection de matière gazeuse, liquide ou solide finement divisée (poudre dont la taille des particules est typiquement supérieure à 100 microns) sous le dôme dans la zone interne permettent la formation d'un acier de composition chimique différente de celle de l'acier de base, coulé dans la zone externe. [0010] Par ailleurs, il est connu que les traitements thermomécaniques classiques visant à augmenter les caractéristiques mécaniques d'un acier, par exemple par la microstructure (martensite, bainite, etc.) ou par une précipitation endogène, possèdent l'inconvénient que la structure de l'acier obtenu finalement peut être altérée par un post-traitement thermique du produit (par exemple soudage, galvanisation, etc.). Il serait dès lors souhaitable, au moins dans certains cas de pouvoir couler directement un produit dont la structure et par conséquent les propriétés mécaniques soient stables tout au long des traitements ultérieurs que pourrait subir le produit.[0009] The continuous casting of steel products of mixed or two-component chemical composition has also aroused great interest in a large number of specific applications, both for long products and for flat products (for example reduction of the silicon content on the surface of the slabs, in order to improve the galvanizing ability of the rolled products, modification of the carbon content at the surface of the peritectic steels to improve their flowability, casting of products whose mechanical properties vary along their thickness, such as high surface strength and high ductility, etc.). The term "bicomponent" refers to products whose chemical composition of steel is different according to the place of the investigated product, for example different in skin relative to the heart. To meet this need, the Applicant has proposed, in the international application WO-A-02/30598, a continuous casting nozzle having in its upper part a dome-shaped distributor device designed to separate the liquid steel in two jets, a internal jet and an external jet, in two physically separated areas. Finely divided gaseous, liquid or solid material injecting means (powder of which the particle size is typically greater than 100 microns) under the dome in the inner zone allow the formation of a steel of different chemical composition from that of the base steel, poured into the outer zone. Furthermore, it is known that conventional thermomechanical treatments to increase the mechanical characteristics of a steel, for example by the microstructure (martensite, bainite, etc.) or endogenous precipitation, have the disadvantage that the structure of the steel finally obtained can be altered by a thermal after-treatment of the product (eg welding, galvanizing, etc.). It would therefore be desirable, at least in certain cases, to be able to directly cast a product whose structure and consequently the mechanical properties are stable throughout the subsequent treatments that the product could undergo.
Buts de l ' inventionGoals of the invention
[0011] La présente invention vise à fournir une solution qui permette de s ' affranchir des inconvénients de l'état de la technique.The present invention aims to provide a solution that allows to overcome the disadvantages of the state of the art.
[0012] La présente invention vise en particulier à fournir un procédé de coulée en continu qui permette d'obtenir des brames ou des billettes de composition chimique adaptée pour conférer à l ' acier une plus grande résistance mécanique avant laminage.The present invention is aimed in particular at providing a continuous casting process which makes it possible to obtain slabs or billets of composition adapted to impart to the steel a greater mechanical strength before rolling.
[0013] L'invention vise notamment à obtenir un acier de composition chimique homogène et/ou de structure stabilisée vis-à-vis d'un procédé de laminage et/ou de traitement thermomécanique postérieur à la coulée. [0014] Un but particulier de la présente invention est d'exploiter la technique du jet creux pour injecter au travers de la busette de coulée continue des particules de céramique finement divisées .The invention aims in particular to obtain a steel of homogeneous chemical composition and / or stabilized structure vis-à-vis a rolling process and / or thermomechanical treatment after casting. A particular object of the present invention is to use the hollow jet technique to inject through the continuous casting nozzle finely divided ceramic particles.
Principaux éléments caractéristiques de l ' inventionMain characteristic elements of the invention
[0015] Un premier objet de la présente invention se rapporte à un procédé pour la coulée continue d'un métal sous forme d'un jet creux dans une busette sise entre une poche de coulée ou un panier répartiteur et une lingotière de coulée continue, ladite busette comprenant dans sa partie supérieure un organe répartiteur capable de dévier au moins une partie du métal liquide arrivant à l'entrée de la busette vers une- paroi interne de la busette avant que celui-ci ne pénètre dans la lingotière, ledit procédé comprenant une inj'ection dans un volume intérieur du jet creux de matière solide finement divisée, caractérisé en ce que la matière solide finement divisée comprend des nanoparticules de céramique technique, de taille caractéristique inférieure à 200 nm et de préférence à 100 nm.A first object of the present invention relates to a method for the continuous casting of a metal in the form of a hollow jet in a nozzle located between a ladle or a tundish and a continuous casting mold, said nozzle comprising in its upper part a distributor member capable of deflecting at least a portion of the liquid metal arriving at the inlet of the nozzle towards an inner wall of the nozzle before it enters the ingot mold, said method comprising an injection into an interior volume of the hollow jet of finely divided solid material, characterized in that the finely divided solid material comprises technical ceramic nanoparticles, of characteristic size less than 200 nm and preferably 100 nm.
[0016] Avantageusement, les nanoparticules de céramique technique comprennent des nanoparticules d'oxydes, de nitrures, de carbures, de borures, de siliciures et/ou des composés de ceux-ci.[0016] Advantageously, the technical ceramic nanoparticles comprise nanoparticles of oxides, nitrides, carbides, borides, silicides and / or compounds thereof.
[0017] De préférence, les oxydes sont Al2O3, TiO2, SiO2, MgO, ZrO2 ou Y2O3. [0018] Toujours avantageusement, la taille des nanoparticules est comprise entre 10 et 100 nm. [0019] Toujours selon l'invention, la quantité de nanoparticules incorporées dans le métal liquide est inférieure ou égale à 5 pour cent, de préférence comprise entre 0,1 et 1 pour cent, en poids de métal coulé. [0020] Selon un mode d'exécution préféré de l'invention, les nanoparticules de céramique injectées dans le volume intérieur du jet creux de la busette sont en suspension dans un gaz non oxydant, de préférence de l'argon, ledit gaz étant en légère surpression par rapport à la pression atmosphérique et au plus égale à la pression statique du métal coulé à l'entrée de celui-ci dans la lingotière. [0021] Selon un autre mode d'exécution préféré de l'invention, les nanoparticules de céramique sont injectées dans le volume intérieur du jet creux de la busette au moyen d'un dispositif mécanique de transport tel qu'une vis sans fin. [0022] De manière particulièrement avantageuse, les nanoparticules sont agglomérées, préalablement à leur injection dans la' busette, en microparticules de taille essentiellement comprise entre 10 et 1000 microns, de préférence entre 100 et 200 microns. [0023] Tout aussi avantageusement, préalablement à l'injection dans la busette, les nanoparticules sont agglomérées dans une matrice métallique constituée ou non du même métal que le métal coulé. [0024] De préférence, le métal coulé est de l'acier liquide et la matrice métallique une matrice de fer ou la matrice métallique comprend un métal d'alliage autre que le fer.[0017] Preferably, the oxides are Al 2 O 3 , TiO 2 , SiO 2 , MgO, ZrO 2 or Y 2 O 3 . Still advantageously, the size of the nanoparticles is between 10 and 100 nm. Still according to the invention, the amount of nanoparticles incorporated in the liquid metal is less than or equal to 5 percent, preferably between 0.1 and 1 percent, by weight of cast metal. According to a preferred embodiment of the invention, the ceramic nanoparticles injected into the interior volume of the hollow jet of the nozzle are suspended in a non-oxidizing gas, preferably argon, said gas being slight overpressure with respect to the atmospheric pressure and at most equal to the static pressure of the metal cast at the inlet thereof into the mold. According to another preferred embodiment of the invention, the ceramic nanoparticles are injected into the interior volume of the hollow jet of the nozzle by means of a mechanical transport device such as a worm. Particularly advantageously, the nanoparticles are agglomerated, prior to their injection into the nozzle, into microparticles of size essentially between 10 and 1000 microns, preferably between 100 and 200 microns. Just as advantageously, prior to injection into the nozzle, the nanoparticles are agglomerated in a metal matrix or not of the same metal as the cast metal. [0024] Preferably, the cast metal is liquid steel and the metal matrix is an iron matrix or the metal matrix comprises an alloy metal other than iron.
[0025] Encore avantageusement, l'agglomération des nanoparticules est obtenue par mélange de nanoparticules de céramique avec des particules micrométriques de fer, c'est- à-dire de taille supérieure à 10 microns, et de préférence inférieure à 20 microns.[0025] Still advantageously, the agglomeration of the nanoparticles is obtained by mixing nanoparticles of ceramic with micrometric particles of iron, that is to say of size greater than 10 microns, and preferably less than 20 microns.
[0026] Selon une première modalité préférée, ledit mélange est réalisé par un mélange préalable dans une barbotine, suivi d'un séchage, d'un broyage, d'un pressage isostatique et d'un rebroyage.According to a first preferred embodiment, said mixture is made by premixing in a slurry, followed by drying, milling, isostatic pressing and regrinding.
[0027] Selon une deuxième modalité préférée, ledit mélange est réalisé par un battage à haute énergie de type "mechanical alloying" pour obtenir une insertion des céramiques dans la matrice de fer.According to a second preferred embodiment, said mixture is made by a high energy hype of "mechanical alloying" type to obtain an insertion of ceramics in the iron matrix.
[0028] Selon un premier mode de réalisation avantageux, la busette à jet creux utilisée est du type à jet tournant, c'est-à-dire composée d'un conduit vertical comprenant dans sa partie supérieure un organe répartiteur à dôme, dont la fonction est de dévier le métal liquide entrant dans la busette vers la surface intérieure dudit conduit et qui comporte une pluralité de bras disposés symétriquement en étoile par rapport à l ' axe de la busette et inclinés par rapport à l'horizontale, lesdits bras étant configurés pour imprimer à l'acier liquide un mouvement tournant hélicoïdal le long de la paroi interne de la busette. [0029] Selon un autre mode de réalisation avantageux, la busette à jet creux utilisée présente dans sa partie supérieure un organe répartiteur à dôme conçu pour séparer le métal liquide en deux jets, un jet interne et un jet externe, dans deux zones physiquement bien séparées, l'injection de nanoparticules de céramique sous le dôme dans la zone interne permettant la formation d'un métal de composition chimique différente de celle du métal de base, coulé dans la zone externe. [0030] Alternativement, l'injection ' • de nanoparticules de céramique peut être effectuée dans la zone externe de la busette.According to a first advantageous embodiment, the hollow jet nozzle used is of the rotating jet type, that is to say composed of a vertical duct comprising in its upper part a dome-shaped distribution member, whose function is to divert the liquid metal entering the nozzle to the inner surface of said conduit and which has a plurality of arms symmetrically arranged in a star with respect to the axis of the nozzle and inclined relative to the horizontal, said arms being configured for printing on the liquid steel a helical twist movement along the inner wall of the nozzle. According to another advantageous embodiment, the hollow jet nozzle used has in its upper part a dome-shaped distributor member designed to separate the liquid metal into two jets, an inner jet and an outer jet, in two physically good zones. separated, the injection of ceramic nanoparticles under the dome in the inner zone allowing the formation of a metal of chemical composition different from that of the base metal, cast in the outer zone. [0030] Alternatively, injection '• ceramic nanoparticles can be performed in the outer area of the nozzle.
[0031] Un second objet de la présente invention se rapporte à un métal, de préférence un acier, de haute résistance mécanique se présentant après coulée sous la forme d'un lingot en brin continu à la sortie d'une lingotière de coulée continue, spécialement obtenu au moyen du procédé décrit ci-dessus, et comprenant moins d'un pour cent en poids de céramique technique répartie de manière homogène dans au moins une partie du lingot.A second subject of the present invention relates to a metal, preferably a steel, of high mechanical strength occurring after casting in the form of a continuous strand ingot at the outlet of a continuous casting mold, specially obtained by the method described above, and comprising less than one percent by weight of technical ceramic homogeneously distributed in at least a portion of the ingot.
Description d'une forme d'exécution préférée de l'invention [0032] L'idée à la base de l'invention est de développer un acier durci par une fine dispersion de particules céramiques conférant à l'acier des propriétés stables et inaltérables par le ou les traitements thermiques ultérieurs .DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION [0032] The idea underlying the invention is to develop a steel hardened by a fine dispersion of ceramic particles giving the steel stable and unalterable properties. the subsequent thermal treatment (s).
[0033] A titre d'exemple, on traitera le cas de la coulée continue d'acier.For example, we will deal with the case of continuous steel casting.
[0034] On propose dès lors de couler un acier de base standard dans lequel est ajouté à la demande une quantité de particules nécessaire pour obtenir les propriétés de résistance demandées. Avantageusement, l'ajout de particules dans le métal liquide est réalisé directement au niveau de la busette de coulée continue, puisque celle-ci, dans les formes d'exécution généralement employées, et décrites ci-dessus, comporte généralement des moyens pour l'introduction d'éléments d'alliage ou d'oxydes dans au moins une fraction du métal liquide traversant la busette.It is therefore proposed to cast a standard base steel in which is added on demand a quantity of particles necessary to obtain the required strength properties. Advantageously, the addition of particles in the liquid metal is carried out directly at the level of the continuous casting nozzle, since this, in the embodiments generally employed, and described above, generally comprises means for the introduction of alloying elements or oxides in at least a fraction of the liquid metal passing through the nozzle.
[0035] Selon l'invention, les particules ajoutées sont des particules céramiques. Il est connu de l'homme de métier qu'on nomme par céramiques techniques ou industrielles une classe de matériaux manufacturés qui sont non-métalliques et inorganiques . Ils se répartissent en deux grandes familles : les oxydes (par exemple Al2O3, TiCb,According to the invention, the added particles are ceramic particles. It is known to those skilled in the art that they are called technical ceramics or industrial class of manufactured materials that are non-metallic and inorganic. They are divided into two major families: oxides (for example Al 2 O 3 , TiCb,
SiÛ2, MgO, ZrO2, Y2O3, etc.) et les non-oxydes (nitrures, carbures, borures, siliciures, etc.). En outre, pour les besoins de l'invention, les particules céramiques devront répondre à la définition opérationnelle suivante : elles sont de taille nanométrique, typiquement 10-100 nanomètresSiO 2 , MgO, ZrO 2 , Y 2 O 3 , etc.) and non-oxides (nitrides, carbides, borides, silicides, etc.). In addition, for the purposes of the invention, the ceramic particles will have to meet the following operational definition: they are of nanometric size, typically 10-100 nanometers
(lnm = 10~9 m) et sont, après incorporation dans l'acier liquide, réparties de manière essentiellement homogène dans toute la section du produit coulé. La "taillé" des particules doit être comprise ici comme étant la dimension la plus grande de la particule. La nature nanométrique des particules d'inclusion est en effet indispensable au renforcement du produit. A l'inverse, des inclusions micrométriques constituent des défauts, des hétérogénéités qui rendent le produit plus fragile.(lnm = 10 ~ 9 m) and are, after incorporation in the liquid steel, distributed substantially homogeneously throughout the section of the cast product. The "cut" of the particles must be understood here as being the largest dimension of the particle. The nanometric nature of the inclusion particles is indeed essential for the reinforcement of the product. Conversely, micrometric inclusions are defects, heterogeneities that make the product more fragile.
[0036] Les quantités de nanoparticules ajoutées à l'acier liquide sont de 1 pour cent maximum en poids. [0037] La mouillabilité des particules dans l'acier liquide est le critère le plus important pour le choix des particules et la résolution de ce problème technique est au cœur de la présente invention. Une répartition homogène des nanoparticules dans l'acier liquide est indispensable, ce qui exclut un confinement des poudres injectées à la surface de l'acier liquide.The amounts of nanoparticles added to the liquid steel are 1 percent by weight. The wettability of the particles in the liquid steel is the most important criterion for the choice of particles and the resolution of this technical problem is at the heart of the present invention. A homogeneous distribution of the nanoparticles in the liquid steel is essential, which excludes a confinement of the powders injected on the surface of the liquid steel.
[0038] Selon l'invention, les particules peuvent être avantageusement agglomérées jusqu'à une taille de 100- 200 |im pour pouvoir être injectées au travers de la busette HJN.According to the invention, the particles may advantageously be agglomerated to a size of 100-200 μm to be injected through the nozzle HJN.
[0039] Pour améliorer la mouillabilité des particules dans l'acier liquide, on peut agglomérer les particules céramiques nanométriques dans une matrice de fer ou métallique pour obtenir un composé dont la taille finale caractéristique est de 100-200 μm. La matrice de fer ou métallique favorise la dispersion des particules dans l'acier liquide. Pour obtenir ce composé, on utilise des particules nanométriques de céramique mélangées à des particules micrométriques de , fer (dont la taille est par exemple de 10 à 20 microns) . Le mélange est réalisé soit par : - mélange dans une barbotine puis séchage, broyage, pressage isostatique et rebroyage ; battage à haute énergie (mechanical alloying) pour obtenir une insertion des céramiques dans la matrice de fer. Le battage est une opération de mise en contact et introduction d'un élément dans un ensemble formé d'un ou de plusieurs éléments différents du premier élément en exerçant un effort sur l'élément.To improve the wettability of the particles in the liquid steel, the nanoscale ceramic particles can be agglomerated in an iron matrix. or metal to obtain a compound whose characteristic final size is 100-200 μm. The iron or metal matrix promotes the dispersion of the particles in the liquid steel. To obtain this compound, nanometric particles of ceramic mixed with micrometric particles of iron (the size of which is for example 10 to 20 microns) are used. The mixture is produced either by: - mixing in a slip, followed by drying, grinding, isostatic pressing and regrinding; high-energy hitting (mechanical alloying) to obtain an insertion of ceramics into the iron matrix. Threshing is an operation of bringing into contact and introducing an element into an assembly formed of one or more different elements of the first element by exerting a force on the element.
[0040] Ces composés sont avantageusement injectés sous atmosphère gazeuse dans la busette HJN (voir brevet EP-B-605 379) . Une forte agitation régnant dans la busette permet alors une bonne insertion des particules dans l'acier liquide. These compounds are advantageously injected under a gas atmosphere into the HJN nozzle (see EP-B-605 379). A strong agitation prevailing in the nozzle then allows a good insertion of the particles in the liquid steel.

Claims

REVENDICATIONS
1. Procédé pour la coulée continue d' un métal sous forme d'un jet creux dans une busette sise entre une poche de coulée ou un panier répartiteur et une lingotière de coulée continue, ladite busette comprenant dans sa partie supérieure un organe répartiteur capable de dévier au moins une partie du métal liquide arrivant à l'entrée de la busette vers une paroi interne de la busette avant que celui-ci ne pénètre dans la lingotière, ledit procédé comprenant une injection dans un volume intérieur du jet . creux de matière solide finement divisée, caractérisé en ce que la matière solide finement divisée comprend, des nanoparticules de céramique technique, de taille caractéristique inférieure à 200 nm et de préférence à 100 nm.1. A method for the continuous casting of a metal in the form of a hollow jet in a nozzle located between a pouring ladle or a tundish and a continuous casting mold, said nozzle comprising in its upper part a distribution member capable of deflecting at least a portion of the liquid metal arriving at the inlet of the nozzle to an inner wall of the nozzle before it enters the mold, said method comprising an injection into an interior volume of the jet. hollow finely divided solid material, characterized in that the finely divided solid material comprises technical ceramic nanoparticles of characteristic size less than 200 nm and preferably 100 nm.
2. Procédé selon la revendication 1, caractérisé en ce que les nanoparticules de céramique technique comprennent des nanoparticules d'oxydes, de nitrures, de carbures, de borures, de siliciures et/ou des composés de ceux-ci.2. Method according to claim 1, characterized in that the technical ceramic nanoparticles comprise nanoparticles of oxides, nitrides, carbides, borides, silicides and / or compounds thereof.
3. Procédé selon la revendication 2, caractérisé en ce' que les oxydes sont AI2O3, TiO2, SiO2, MgO, ZrO2 ou Y2O3.3. Method according to claim 2, characterized in that the oxides are Al 2 O 3 , TiO 2 , SiO 2 , MgO, ZrO 2 or Y 2 O 3 .
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la taille des nanoparticules est comprise entre 10 et 100 nm.4. Method according to any one of claims 1 to 3, characterized in that the size of the nanoparticles is between 10 and 100 nm.
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la quantité de nanoparticules incorporées dans le métal liquide est inférieure ou égale à 5 pour cent , de préférence comprise entre 0,1 et 1 pour cent, en poids de métal coulé.5. Method according to any one of the preceding claims, characterized in that the amount of nanoparticles incorporated in the liquid metal is less than or equal to 5 percent, preferably between 0.1 and 1 percent, by weight of metal. sank.
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les nanoparticules de céramique injectées dans le volume intérieur du jet creux de la busette sont en suspension dans un gaz non oxydant, de préférence de l'argon, ledit gaz étant en légère surpression par rapport à la pression atmosphérique et au plus égale à la pression statique du métal coulé à l'entrée de celui-ci dans la lingotière.6. Method according to any one of the preceding claims, characterized in that the ceramic nanoparticles injected into the interior volume of the hollow jet of the nozzle are suspended in a non-oxidizing gas, preferably argon, said gas being slightly overpressured with respect to the atmospheric pressure and at most equal to the static pressure cast metal at the inlet thereof in the mold.
7. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les nanoparticules de céramique sont injectées dans le volume intérieur du jet creux de la busette au moyen d'un dispositif mécanique de transport tel qu'une vis sans fin.7. Method according to any one of claims 1 to 5, characterized in that the ceramic nanoparticles are injected into the interior volume of the hollow jet of the nozzle by means of a mechanical transport device such as a worm .
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les nanoparticules sont agglomérées, préalablement à leur injection dans la busette, en microparticules de taille essentiellement comprise entre 10 et 1000 microns, de préférence entre 100 et 200 microns.8. Process according to any one of the preceding claims, characterized in that the nanoparticles are agglomerated, prior to their injection into the nozzle, into microparticles of size essentially between 10 and 1000 microns, preferably between 100 and 200 microns.
9. Procédé selon la revendication 8, caractérisé en ce que, préalablement à l'injection dans la busette, les nanoparticules sont agglomérées dans une matrice métallique constituée ou non du même métal que le métal coulé.9. The method of claim 8, characterized in that, prior to injection into the nozzle, the nanoparticles are agglomerated in a metal matrix or not of the same metal as the cast metal.
10. Procédé selon la revendication 9, caractérisé en ce que le métal coulé est de l'acier liquide et la matrice métallique une matrice de fer.10. The method of claim 9, characterized in that the cast metal is liquid steel and the metal matrix an iron matrix.
11. Procédé selon la revendication 10, caractérisé en ce que la matrice métallique comprend un métal d'alliage autre que le fer.11. The method of claim 10, characterized in that the metal matrix comprises an alloy metal other than iron.
12. Procédé selon la revendication 10 ou 11, caractérisé en ce que l'agglomération des nanoparticules est obtenue par mélange de nanoparticules de céramique avec des particules micrométriques de fer, c'est-à-dire de taille supérieure à 10 microns, et de préférence inférieure à 20 microns. 12. The method of claim 10 or 11, characterized in that the agglomeration of the nanoparticles is obtained by mixing ceramic nanoparticles with micrometric iron particles, that is to say larger than 10 microns, and preferably less than 20 microns.
13. Procédé selon la revendication 12, caractérisé en ce que ledit mélange est réalisé par un mélange préalable dans une barbotine, suivi d'un séchage, d'un broyage, d'un pressage isostatique et d'un rebroyage. 13. The method of claim 12, characterized in that said mixing is carried out by premixing in a slip, followed by drying, grinding, isostatic pressing and regrinding.
14. Procédé selon la revendication 12, caractérisé en ce que ledit mélange est réalisé par un battage à haute énergie de type "mechanical alloying" pour obtenir une insertion des céramiques dans la matrice de fer. 14. The method of claim 12, characterized in that said mixture is made by a high energy hype of "mechanical alloying" type to obtain an insertion of ceramics in the iron matrix.
15. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la busette à jet creux utilisée est du type à jet tournant, c'est-à-dire composée d'un conduit vertical comprenant dans sa partie supérieure un organe répartiteur à dôme, dont la fonction est de . dévier le métal liquide entrant dans la busette vers la surface intérieure dudit conduit et qui comporte une pluralité de bras disposés symétriquement en étoile par rapport à l'axe de la busette et inclinés par rapport à l'horizontale, lesdits bras étant configurés pour imprimer à l'acier liquide un mouvement tournant hélicoïdal le long de la paroi interne de la busette.15. Method according to any one of the preceding claims, characterized in that the hollow jet nozzle used is of the rotary jet type, that is to say composed of a vertical duct comprising in its upper part a distributor member dome, whose function is to. deflecting the liquid metal entering the nozzle towards the inner surface of said duct and which comprises a plurality of arms arranged symmetrically in a star with respect to the axis of the nozzle and inclined relative to the horizontal, said arms being configured to print at the liquid steel a helical twist movement along the inner wall of the nozzle.
16. Procédé selon l'une quelconque des revendications 1 à 14, caractérisé, en ce que la busette à jet creux utilisée présente dans sa partie supérieure un organe répartiteur à dôme conçu pour séparer le métal liquide en deux jets, un jet interne et un jet externe, dans deux zones physiquement bien séparées, l'injection de nanoparticules . de céramique sous le dôme dans la zone interne permettant la formation d'un métal de composition chimique différente de celle du métal de base, coulé dans la zone externe.16. A method according to any one of claims 1 to 14, characterized in that the hollow jet nozzle used has in its upper part a dome-shaped distribution device designed to separate the liquid metal in two jets, an internal jet and a external jet, in two physically well separated areas, the injection of nanoparticles. ceramic under the dome in the inner zone allowing the formation of a metal of chemical composition different from that of the base metal, cast in the outer zone.
17. Procédé selon la revendication 16, caractérisé en ce que l'injection de nanoparticules de céramique est effectuée alternativement dans la zone externe .17. Process according to claim 16, characterized in that the injection of nanoparticles ceramic is performed alternately in the outer zone.
18. Métal, de préférence acier, de haute résistance mécanique se présentant après coulée sous la forme d'un lingot en brin continu à la sortie d'une lingotière de coulée continue, pouvant être obtenu au moyen du procédé selon l'une quelconque des revendications précédentes, comprenant moins d'un pour cent en poids de céramique technique répartie de manière homogène dans au moins une partie du lingot. 18. Metal, preferably steel, of high mechanical strength occurring after casting in the form of a continuous strand ingot at the outlet of a continuous casting mold, obtainable by means of the process according to any one of preceding claims, comprising less than one percent by weight of technical ceramic homogeneously distributed in at least a portion of the ingot.
EP06701517A 2005-03-16 2006-01-19 Method for continuous casting of a metal with improved mechanical strength and product obtained by said method Not-in-force EP1858662B1 (en)

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