EP0281485B1 - Composite product in a tubular envelope for treating molten-metal baths - Google Patents

Composite product in a tubular envelope for treating molten-metal baths Download PDF

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Publication number
EP0281485B1
EP0281485B1 EP88420033A EP88420033A EP0281485B1 EP 0281485 B1 EP0281485 B1 EP 0281485B1 EP 88420033 A EP88420033 A EP 88420033A EP 88420033 A EP88420033 A EP 88420033A EP 0281485 B1 EP0281485 B1 EP 0281485B1
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EP
European Patent Office
Prior art keywords
formed body
composite formed
casing
pulverulent
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP88420033A
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German (de)
French (fr)
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EP0281485A1 (en
Inventor
Michel Douchy
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Affival SA
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Affival SA
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Priority to AT88420033T priority Critical patent/ATE57541T1/en
Publication of EP0281485A1 publication Critical patent/EP0281485A1/en
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12069—Plural nonparticulate metal components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/1209—Plural particulate metal components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12097—Nonparticulate component encloses particles

Definitions

  • the object of the invention relates to a composite product with a tubular casing for the treatment of molten metal baths as well as to a process for the implementation of this product.
  • This composite product for the treatment of molten metal baths which is described in the utility certificate FR.2433.584.
  • This composite product called cored wire in this document, comprises in particular a metal sheath or envelope constituted by a thin strip of great length, the edges of which are curved so as to obtain by approximation or by welding a substantially circular section. Inside this sheath is housed a pulverulent or granular material such as, for example, a powder of Ca Si alloy.
  • a cored wire, 12 mm in diameter, for a sheath thickness of 0.5 mm is introduced, by example in a pocket of liquid steel at a speed of 2m / sec. (FR 2,433,584 page 4).
  • a steel bath in a pocket is treated with a composite product with a steel casing, introduced approximately vertically into the bath, the depth of penetration depends on the thickness of the casing and the speed of introduction but the residence time is very short because as soon as the melting temperature of the envelope is reached it is dissolved almost instantaneously.
  • the content of the cored wire consists of low volatility addition elements, such as Si, Mn, Ti
  • a premature release of these has no significant drawbacks.
  • they are highly volatile elements such as Ca or Mg, a release at a shallow depth causes very significant yield losses.
  • the phenomenon of premature melting of the envelope is observed particularly strikingly when this envelope has a melting temperature much lower than the temperature of the metal bath. This is for example the case of the treatment of liquid steel with a composite product with an aluminum envelope.
  • the composite product which is the subject of the invention makes it possible to treat metal baths in depth.
  • the method which is also the subject of the invention, makes it possible in particular to desulfurize the steel or cast iron baths, with particularly high efficiency, thanks to the release in two successive stages of the content of the composite product during its penetration into such baths.
  • This composite product is composed of a very long tubular metal casing inside which are housed the powdery or granular material or materials for the treatment of molten metal baths, this product being introduced into these metal baths.
  • This composite product comprises, inside the tubular envelope, an axial zone containing at least one first pulverulent or granular material surrounded by an intermediate metallic tubular wall.
  • An annular zone, between the intermediate tubular wall and the tubular envelope, also contains at least one second pulverulent or granular material.
  • the envelope and the intermediate wall are made of metals compatible with the bath to be treated.
  • the envelope will have a substantially circular shape, as will the intermediate wall.
  • the tubular casing and the intermediate wall may be produced, depending on the case, either in the same metal or in different metals, the na ture thereof or thereof being compatible with the bath to be treated and the thickness of the envelope and the wall being determined according to the conditions corresponding to each application.
  • the na ture thereof or thereof being compatible with the bath to be treated
  • the thickness of the envelope and the wall being determined according to the conditions corresponding to each application.
  • at least the axial zone of the composite product contains at least one element chosen from calcium and magnesium alloyed or unalloyed.
  • the second pulverulent or granular material may have all or part of the same composition as the first pulverulent or granular material. However, such a case will generally be quite rare.
  • the invention also relates to a method of treating metal baths using the product according to the invention.
  • the composition of the first and second pulverulent or granular materials is adjusted so that the axial zone contains at least for the most part the material (s) most reactive or most volatile with respect to the bath to be treated.
  • the method applies in particular to the desulfurization treatment of steels and cast irons.
  • these metals are treated by means of the composite product according to the invention, at least the axial zone thereof containing in the alloyed or unalloyed state magnesium and / or calcium.
  • the annular zone of this same composite product contains one or more materials ensuring additional desulphurization such as for example MgO, CaO, Ca COa, Na 2 COa, Ca C 2 in powder or granular form.
  • additional desulfurization material is combined with aluminum in granular form or not.
  • This second material included in the annular zone can also comprise complementary products to compensate for the elements of the metal bath which disappear during a thorough desulfurization of the metal, such as for example silicon.
  • the composite product according to the invention can be produced by any method known to those skilled in the art.
  • edges of the strips forming the intermediate wall and the envelope can be closed by any known means compatible with the pulverulent or granular materials used: edge-to-edge approximation, covering, stapling or the like.
  • edge-to-edge approximation covering, stapling or the like.
  • seamless tubes their filling being however more difficult.
  • the material contained, both in the axial zone and in the annular zone, is preferably compacted by also known means such as compression, stretching or the like.
  • the product according to the invention retains significant rigidity during its penetration into a metal bath.
  • the material which fills the annular zone plays the role of an effective insulator which considerably slows down the rise in temperature of the intermediate wall. It therefore retains a significant fraction of its mechanical characteristics. It therefore cooperates with the content of the axial zone to resist the forces which tend to deform it in bending and also to the hydrostatic thrust which tends to prevent it from sinking into the metal bath. It is only from the moment when this intermediate wall comes into direct contact with the metal bath, following the dissolution or fusion of the envelope, that the temperature of this wall rises very quickly and that its mechanical characteristics collapse.
  • the envelope must preferably be made of a metal whose melting temperature is at least equal to that of the metal from which the intermediate wall is made.
  • the sections of the axial zone and of the annular zone are determined on the basis of the respective volumes of the materials which it is intended to accommodate therein.
  • the metal and the thickness of the envelope must be determined so that the time required for its fusion, or complete dissolution, corresponds, taking into account the speed of penetration of the composite product into the metal bath, at the depth at which wants to release the material contained in the annular zone.
  • the single figure represents a composite product (1), according to the invention, of substantially circular section with axis (0). It has an outer casing (2) of steel 14 mm in external diameter and 0.3 mm thick.
  • the intermediate steel wall (3) is 9 mm outside diameter and 0.4 mm thick.
  • the axial zone (4) contains grains of unalloyed calcium about 0.5 mm in diameter.
  • the intermediate wall closed by simple covering in (5), was slightly tightened on its content by reducing its outside diameter by about 25% by passage through a die.
  • the annular zone (6) is filled with iron powder.
  • the outer envelope which is stapled at (7) is also tightened on its contents.
  • This compost product is treated with 65 tonnes of liquid steel contained in a ladle bag at a temperature of 1580 ° C. to desulfurize the metal.
  • the measurements on composite product extracted from the bath make it possible to estimate the difference in height between the two points of passage in the bath of the outer tubular casing and of the intermediate tubular wall at 50 to 60 cm.
  • the value measured on product removed from the bath very quickly after interruption of the injection is actually lower (38 cm) because the calcium in the axial zone continues to burn in the open air for about one minute.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Coating With Molten Metal (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Laminated Bodies (AREA)
  • Metal Extraction Processes (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a composite product of substantial length for the treatment of metal baths which is formed by a tubular metal casing (2) within which are housed the treatment material or materials in powder form and which comprises an axial zone (4) containing a first material surrounded by a tubular metal intermediate wall (3) and an annular zone (6) between the casing and the intermediate wall and which also contains a second material. Such a composite product in which the axial zone contains at least one element selected from calcium and magnesium can be used in particular for the desulphurization of iron or steel baths.

Description

L'objet de l'invention concerne un produit composite à enveloppe tubulaire pour le traitement des bains métalliques fondus ainsi qu'un procédé pour la mise en oeuvre de ce produit.The object of the invention relates to a composite product with a tubular casing for the treatment of molten metal baths as well as to a process for the implementation of this product.

On connait un produit composite pour le traitement de bains métalliques fondus qui est décrit dans le certificat d'utilité FR.2433.584. Ce produit composite, appelé fil fourré dans ce document, comporte notamment une gaine métallique ou enveloppe constituée par un feuillard mince de grande longueur dont les bords sont recourbés de façon à obtenir par rapprochement ou par soudage une section sensiblement circulaire. A l'intérieur de cette gaine est logée une matière pulvérulente ou granulaire telle qui par exemple une poudre d'alliage Ca Si. Un tel fil fourré, de 12 mm de diamètre, pour une épaisseur de gaine de 0,5mm est introduit, par exemple dans une poche d'acier liquide à une vitesse de 2m/sec. (FR 2.433.584 page 4).There is a known composite product for the treatment of molten metal baths which is described in the utility certificate FR.2433.584. This composite product, called cored wire in this document, comprises in particular a metal sheath or envelope constituted by a thin strip of great length, the edges of which are curved so as to obtain by approximation or by welding a substantially circular section. Inside this sheath is housed a pulverulent or granular material such as, for example, a powder of Ca Si alloy. Such a cored wire, 12 mm in diameter, for a sheath thickness of 0.5 mm is introduced, by example in a pocket of liquid steel at a speed of 2m / sec. (FR 2,433,584 page 4).

L'expérience a montré que, dans beaucoup de cas, pour que le traitement du métal liquide atteigne sa pleine efficacité, le contenu du fil fourré doit pouvoir être introduit jusqu'au fond de la poche contenant le bain métallique. Il est de plus nécessaire que ce contenu soit livéré de son enveloppe au moment où il se trouve au voisinage de ce fond. Si l'enveloppe est détruite de façon prématurée, par exemple par fusion très rapide dès la pénétration dans le vain métallique, son contenu est livéré au voisinage de la surface de ce bain. Dans d'autres cas on peut observer une dissolution relativement lente de l'enveloppe au cours de sa pénétration dans le vain métallique. Mais, à la température à laquelle elle est portée, cette enveloppe perd toute rigidité et se courbe progressivement en U de sorte que son extrémité remonte vers la surface avant que le contenu soit libéré. Une telle remontée est dûe en particulier à la poussée hydrostatique ; en effet la densité apparente du produit composite est en général bien inférieure à celle du bain métallique.Experience has shown that, in many cases, for the treatment of liquid metal to reach its full efficiency, the content of the cored wire must be able to be introduced to the bottom of the pocket containing the metal bath. It is also necessary that this content is delivered from its envelope when it is in the vicinity of this background. If the envelope is destroyed prematurely, for example by very rapid fusion upon penetration into the metallic vain, its content is delivered in the vicinity of the surface of this bath. In other cases one can observe a relatively slow dissolution of the envelope during its penetration in the metallic vain. However, at the temperature to which it is brought, this envelope loses all rigidity and gradually curves in a U so that its end rises towards the surface before the contents are released. Such a rise is due in particular to the hydrostatic thrust; in fact the bulk density of the composite product is generally much lower than that of the metal bath.

Si on traite par exemple un bain d'acier en poche par un produit composite à enveloppe d'acier, introduit à peu près verticalement dans le bain, la profondeur de pénétration dépend de l'épaisseur de l'enveloppe et de la vitesse d'introduction mais le temps de séjour est très court car dès que la température de fusion de l'enveloppe est atteinte celle-ci est dissoute quasi instantanément.If, for example, a steel bath in a pocket is treated with a composite product with a steel casing, introduced approximately vertically into the bath, the depth of penetration depends on the thickness of the casing and the speed of introduction but the residence time is very short because as soon as the melting temperature of the envelope is reached it is dissolved almost instantaneously.

Lorsque le contenu du fil fourré est constitué par des éléments d'addition peu volatils, tels que Si, Mn, Ti, une libération prématurée de ceux-ci n'a pas d'inconvénients notables. Par contre s'il s'agit d'éléments reès volatils tels que Ca ou Mg une libération à faible profondeur entraîne des pertes de rendement très importantes. Le phénomène de fusion prématurée de l'enveloppe est observé de façon particulièrement frappante lorsque cette enveloppe a une température de fusion très inférieure à la température du bain métallique. C'est par exemple le cas du traitement de l'acier liquide par un produit composite à enveloppe d'aluminium.When the content of the cored wire consists of low volatility addition elements, such as Si, Mn, Ti, a premature release of these has no significant drawbacks. On the other hand, if they are highly volatile elements such as Ca or Mg, a release at a shallow depth causes very significant yield losses. The phenomenon of premature melting of the envelope is observed particularly strikingly when this envelope has a melting temperature much lower than the temperature of the metal bath. This is for example the case of the treatment of liquid steel with a composite product with an aluminum envelope.

On a constaté aussi que la mise en oeuvre d'un produit composite dont l'enveloppe a une température de fusion supérieure à la température du bain métallique présente aussi des inconvénients sérieux. En effet dans ce cas, même si l'enveloppe est mince, on n'observe pas de phénomène de fusion quasi immédiate à partir du moment où la température de l'enveloppe est devenue voisine de celle du bain métallique. On observe seulement une dissolution progressive. Le choix d'une épaisseur telle que la dissolution soit complète seulement lorsque le fil fourré a atteint une profondeur déterminée, compte tenu de la vitesse d'introduction, aboutit à un échec. En effet l'enveloppe ayant perdu toute rigidité le fil fourré se recourbe en U et remonte en direction de la surface du bain avant d'avoir libéré son contenu.It has also been found that the use of a composite product whose envelope has a melting temperature higher than the temperature of the metal bath also has serious drawbacks. Indeed in this case, even if the envelope is thin, there is no almost immediate phenomenon of melting from the moment when the temperature of the envelope has become close to that of the metal bath. We only observe a progressive dissolution. The choice of a thickness such that the dissolution is complete only when the cored wire has reached a determined depth, taking into account the speed of introduction, results in failure. Indeed, the envelope having lost all rigidity the cored wire bends in a U and rises in the direction of the surface of the bath before having released its content.

On a recherché la possibilité de réaliser un produit composite qui conserve une rigidité suffisante pour permettre d'introduire au moins une partie de ses composants dans un bain métallique au voisinage du fond du récipient qui le contient et permette également de libérer cette même partie de ses composants de façon aussi complète que possible, au voisinage de ce fond, sans remontée de ce produit composite en direction de la surface du bain.We looked for the possibility of producing a composite product which retains sufficient rigidity to allow the introduction of at least part of its components into a metal bath near the bottom of the container which contains it and also allows this same part to be released from its components as completely as possible, in the vicinity of this bottom, without ascent of this composite product towards the surface of the bath.

On a recherché aussi la possibilité de réaliser un produit composite permettant de libérer dans le bain de métal liquide une part déterminée à l'avance de son contenu à relativement faible profondeur, le reste du contennu étant libéré à plus grande profondeur, de préférence au voisinage du fond du récipient.We also looked for the possibility of producing a composite product allowing to release in the liquid metal bath a predetermined part of its content at relatively shallow depth, the rest of the contents being released at greater depth, preferably in the vicinity from the bottom of the container.

On a recherché enfin la possibilité de mettre au point une méthode de désulfuration des aciers et des fontes faisant appel à un tel produit composite.Finally, we looked for the possibility of developing a method for desulfurization of steels and cast irons using such a composite product.

Le produit composite qui fait l'objet de l'invention permet de traiter en profondeur les bains métalliques.The composite product which is the subject of the invention makes it possible to treat metal baths in depth.

La méthode, qui fait également l'objet de l'invention, permet en particulier de désulfurer les bains d'acier ou de fonte, avec une efficacité particulièrement grande, grâce à la libération en deux étapes successives du contenu du produit composite au cours de sa pénétration dans de tels bains.The method, which is also the subject of the invention, makes it possible in particular to desulfurize the steel or cast iron baths, with particularly high efficiency, thanks to the release in two successive stages of the content of the composite product during its penetration into such baths.

Ce produit composite est composé d'une enveloppe métallique tubulaire de grande longueur à l'intérieur de laquelle sont logées la ou les matières pulvérulentes ou granulaires pour le traitement de bains métalliques fondus, ce produit étant introduit dans ces bains métalliques.This composite product is composed of a very long tubular metal casing inside which are housed the powdery or granular material or materials for the treatment of molten metal baths, this product being introduced into these metal baths.

Ce produit composite comporte, à l'intérieur de l'enveloppe tubulaire, une zone axiale contenant au moins une première matière pulvérulente ou granulaire entourée d'une paroi tubulaire métallique intermédiaire. Une zone annulaire, comprise entre la paroi tubulaire intermédiaire et l'enveloppe tubulaire, contient aussi au moins une deuxième matière pulvérulente ou granulaire.This composite product comprises, inside the tubular envelope, an axial zone containing at least one first pulverulent or granular material surrounded by an intermediate metallic tubular wall. An annular zone, between the intermediate tubular wall and the tubular envelope, also contains at least one second pulverulent or granular material.

L'enveloppe et la paroi intermédiaire sont réalisées dans des métaux compatibles avec le bain à traiter.The envelope and the intermediate wall are made of metals compatible with the bath to be treated.

Préférentiellement l'enveloppe aura une forme sensiblement circulaire de même que la paroi intermédiaire.Preferably, the envelope will have a substantially circular shape, as will the intermediate wall.

L'enveloppe tubulaire et la paroi intermédiaire pourront être réalisées selon les cas soit dans le même métal, soit dans des métaux différents, la nature de celui-ci ou de ceux-ci étant compatible avec le bain à traiter et l'épaisseur de l'enveloppe et de la paroi étant déterminée en fonction des conditions correspondant à chaque application. Par exemple pour traiter des bains d'acier ou de fonte, on pourra choisir comme enveloppe et/ou paroi intermédiaire de l'acier. Avantageusement également au moins la zone axiale du produit composite contient au moins un élément choisi parmi le calcium et le magnésium alliés ou non alliés.The tubular casing and the intermediate wall may be produced, depending on the case, either in the same metal or in different metals, the na ture thereof or thereof being compatible with the bath to be treated and the thickness of the envelope and the wall being determined according to the conditions corresponding to each application. For example, to treat steel or cast iron baths, it is possible to choose as an envelope and / or an intermediate wall of steel. Advantageously also at least the axial zone of the composite product contains at least one element chosen from calcium and magnesium alloyed or unalloyed.

Le cas échéant, la deuxième matière pulvérulente ou granulaire peut avoir en totalité ou en partie la même composition que la première matière pulvérulente ou granulaire. Toutefois un tel cas sera en général assez rare.Where appropriate, the second pulverulent or granular material may have all or part of the same composition as the first pulverulent or granular material. However, such a case will generally be quite rare.

L'invention concerne également une méthode de traitement des bains métalliques au moyen du produit suivant l'invention.The invention also relates to a method of treating metal baths using the product according to the invention.

De façon avantageuse on ajuste la composition des première et deuxième matières pulvérulentes ou granulaires de façon que la zone axiale contienne au moins en majeure partie la ou les matières les plus réactives ou les plus volatiles vis-à-vis du bain à traiter.Advantageously, the composition of the first and second pulverulent or granular materials is adjusted so that the axial zone contains at least for the most part the material (s) most reactive or most volatile with respect to the bath to be treated.

La méthode s'applique en particulier au traitement de désulfuration des aciers et des fontes. De façon avantageuse on traite ces métaux au moyen du produit composite suivant l'invention, au moins la zone axiale de celui-ci contenant à l'état allié ou non allié du magnésium et/ou du calcium.The method applies in particular to the desulfurization treatment of steels and cast irons. Advantageously, these metals are treated by means of the composite product according to the invention, at least the axial zone thereof containing in the alloyed or unalloyed state magnesium and / or calcium.

De façon avantageuse, la zone annulaire de ce même produit composite contient une ou plusieurs matières assurant un complément de désulfuration comme par exemple MgO, CaO, Ca COa, Na2COa, Ca C2 sous forme pulvérulente ou granulaire. De façon préférentielle cette matière complément de désulfuration est associée à de l'aluminium sous forme granulaire ou non.Advantageously, the annular zone of this same composite product contains one or more materials ensuring additional desulphurization such as for example MgO, CaO, Ca COa, Na 2 COa, Ca C 2 in powder or granular form. Preferably, this additional desulfurization material is combined with aluminum in granular form or not.

Cette deuxième matière comprise dans la zone annulaire peut également comprendre des produits de complément pour compenser les éléments du bain métallique qui disparaissent lors d'une désulfuration poussée du métal, comme par exemple le silicium.This second material included in the annular zone can also comprise complementary products to compensate for the elements of the metal bath which disappear during a thorough desulfurization of the metal, such as for example silicon.

Le produit composite suivant l'invention peut être réalisé par toute méthode connue de l'homme de l'art. On peut réaliser dans une première phase la zone axiale de ce produite entourée de sa paroi intermédiaire en utilisant par exemple un feuillard à bords rapprochés ou à bords agrafés ou à bords se recouvrant l'un l'autre. On peut ensuite, dans une deuxième phase, réaliser l'enveloppe tubulaire extérieure enfermant sa zone axiale et sa zone annulaire, le produit composite qui a été réalisé dans la première phase étant noyé dans la matière qui remplira la zone annulaire, l'ensemble étant, à nouveau, entouré par une enveloppe formée à partir d'un feuillard mince. Comme le sait l'homme de l'art, les bords des feuillards formant la paroi intermédiaire et l'enveloppe peuvent être fermés par tout moyen connu compatible avec les matières pulvérulentes ou granulaires utilisées : rapprochement bord à bord, recouvrement, agrafage ou autre. On peut envisager aussi d'utiliser des tubes sans soudure, leur remplissage étant cependant plus difficile. La matière contenue, aussi bien dans la zone axiale que dans la zone annulaire, est, de préférence, compactée par des moyens également connus tels que compression, étirage ou autre. On peut en particulier utiliser une méthode telle que celle décrite dans le brevet EP.34994 qui consiste à déformer l'enveloppe à périmètre constant de façon à obtenir deux zones aplaties parallèles. Toute autre méthode peut également être utilisée.The composite product according to the invention can be produced by any method known to those skilled in the art. One can realize in a first phase the axial area of this product surrounded by its intermediate wall using for example a strip with close edges or stapled edges or edges overlapping each other. It is then possible, in a second phase, to produce the outer tubular envelope enclosing its axial zone and its annular zone, the composite product which has been produced in the first phase being embedded in the material which will fill the annular zone, the assembly being , again, surrounded by an envelope formed from a thin strip. As those skilled in the art know, the edges of the strips forming the intermediate wall and the envelope can be closed by any known means compatible with the pulverulent or granular materials used: edge-to-edge approximation, covering, stapling or the like. One can also consider using seamless tubes, their filling being however more difficult. The material contained, both in the axial zone and in the annular zone, is preferably compacted by also known means such as compression, stretching or the like. One can in particular use a method such as that described in patent EP.34994 which consists in deforming the envelope at constant perimeter so as to obtain two flattened parallel zones. Any other method can also be used.

L'expérience a montré que grâce à sa structure particulière, le produit suivant l'invention conserve une rigidité importante au cours de sa pénétration dans un bain métallique. En effet tant que l'enveloppe tubulaire n'est pas détruite par dissolution la matière qui remplit la zone annulaire joue le rôle d'un calorifuge efficace qui ralentit considérablement la montée en température de la paroi intermédiaire. Celle-ci conserve donc une importante fraction de ses caractéristiques mécaniques. Elle coopère donc avec le contenu de la zone axiale pour résister aux forces qui tendent à la déformer en flexion et aussi à la poussée hydrostatique qui tend à l'empêcher de s'enfoncer dans le bain métallique. C'est seulement à partir du moment où cette paroi intermédiaire entre en contact direct avec le bain métallique, à la suite de la dissolution ou fusion de l'enveloppe, que la température de cette paroi s'élève très vite et que ses caractéristiques mécaniques s'effondrent.Experience has shown that thanks to its particular structure, the product according to the invention retains significant rigidity during its penetration into a metal bath. In fact, as long as the tubular envelope is not destroyed by dissolution, the material which fills the annular zone plays the role of an effective insulator which considerably slows down the rise in temperature of the intermediate wall. It therefore retains a significant fraction of its mechanical characteristics. It therefore cooperates with the content of the axial zone to resist the forces which tend to deform it in bending and also to the hydrostatic thrust which tends to prevent it from sinking into the metal bath. It is only from the moment when this intermediate wall comes into direct contact with the metal bath, following the dissolution or fusion of the envelope, that the temperature of this wall rises very quickly and that its mechanical characteristics collapse.

L'homme de l'art, par de simples essais de routine, détermine facilement, en fonction notamment de la composition du bain métallique, de sa densité, de sa profondeur et de sa température, les caractéristiques préférentielles qu'il convient de donner à la paroi intermédiaire et à l'enveloppe. L'enveloppe doit de préférence être réalisée dans un métal dont la température de fusion est au moins égale à celle du métal dont est constituée la paroi intermédiaire. Les sections de la zone axiale et de la zone annulaire sont déterminées en fonciton des volumes respectifs des matières qu'on se propse d'y loger. Le métal et l'épaisseur de l'enveloppe doivent être déterminés de façon que le temps nécessaire pour sa fusion, ou dissolution complète, corresponde, compte tenu de la vitesse de pénétration du produit composite dans le bain métallique, à la profondeur à laquelle on veut libérer la matière contenu dans la zone annulaire.Those skilled in the art, by simple routine tests, easily determine, depending in particular on the composition of the metal bath, its density, its depth and its temperature, the preferential characteristics which should be given to the intermediate wall and the envelope. The envelope must preferably be made of a metal whose melting temperature is at least equal to that of the metal from which the intermediate wall is made. The sections of the axial zone and of the annular zone are determined on the basis of the respective volumes of the materials which it is intended to accommodate therein. The metal and the thickness of the envelope must be determined so that the time required for its fusion, or complete dissolution, corresponds, taking into account the speed of penetration of the composite product into the metal bath, at the depth at which wants to release the material contained in the annular zone.

L'exemple et. la figure unique ci-après décrivent de façon non limitative, un produit composite suivant l'invention et un mode particulier de mise en oeuvre de celui-ci.The example and. the single figure below describes in a nonlimiting manner, a composite product according to the invention and a particular mode of implementation thereof.

Figure unique: vue en coupe transversale du produit composite suivant l'invention.Single figure: cross-sectional view of the composite product according to the invention.

La figure unique représente un produit composite (1), suivant l'invention, de section sensiblement circulaire d'axe (0). Il comporte une enveloppe extérieure (2) en acier de 14 mm de diamètre extérieur et 0,3 mm d'épaisseur. La paroi intermédiaire (3) en acier a 9 mm de diamètre extérieur et 0,4mm d'épaisseur. La zone axiale (4) contient des grains de calcium non allié d'environ 0,5 mm de diamètre. La paroi intermédiaire, fermée par simple recouvrement en (5), a été légèrement serrée sur son contenu par réduction de son diamère extérieur d'environ 25 % par passage à travers une filière. La zone annulaire (6) est remplie de poudre de fer. L'enveloppe extérieure qui est agrafée en (7) est également serrée sur son contenu.The single figure represents a composite product (1), according to the invention, of substantially circular section with axis (0). It has an outer casing (2) of steel 14 mm in external diameter and 0.3 mm thick. The intermediate steel wall (3) is 9 mm outside diameter and 0.4 mm thick. The axial zone (4) contains grains of unalloyed calcium about 0.5 mm in diameter. The intermediate wall, closed by simple covering in (5), was slightly tightened on its content by reducing its outside diameter by about 25% by passage through a die. The annular zone (6) is filled with iron powder. The outer envelope which is stapled at (7) is also tightened on its contents.

On traite par ce produit compostie 65 tonnes d'acier liquide contenu dans une poche à une température de 1580° C pour désulfurer le métal.This compost product is treated with 65 tonnes of liquid steel contained in a ladle bag at a temperature of 1580 ° C. to desulfurize the metal.

Par rapport à un traitement fait avec un fil fourré classique constitué d'une enveloppe d'acier de 9 mm de diamètre extérieur et 0,6 mm d'épaisseur contenant des grains de calcium non allié à l'état compacté introduit dans le bain métallique à une vitesse de 110 m/min et pour lequel la désulfuration obtenue est de 26 % en moyenne, on constate avec le produit composite décrit ci-dessus et conforme à l'invention une désulfuration de 46 %, la vitesse d'introduction dans le bain étant de 50 m/min seulement et le temps de traitement du bain étant sensiblement le même.Compared to a treatment made with a conventional cored wire consisting of a steel casing 9 mm outside diameter and 0.6 mm thick containing grains of unalloyed calcium in the compacted state introduced into the metal bath at a speed of 110 m / min and for which the desulfurization obtained is 26% on average, with the composite product described above and in accordance with the invention, there is a desulfurization of 46%, the rate of introduction into the bath being only 50 m / min and the bath treatment time being substantially the same.

Ceci correspond à des quantités de calcium introduites dans le bain de 0,15 Kg/T pour le fil fourré classique et 0,15 Kg/T pour le produit composite selon l'invention.This corresponds to amounts of calcium introduced into the bath of 0.15 Kg / T for the conventional filled wire and 0.15 Kg / T for the composite product according to the invention.

On a pu en évidence, en retirant le fil très rapidement après interruption de llnjection, que le produit composite selon l'invention décrit ci-dessus passe bien dans le bain de métal traité en deux phases correspondant à des profondeurs différentes.It was evident, by removing the wire very quickly after interruption of the injection, that the composite product according to the invention described above passes well into the metal bath treated in two phases corresponding to different depths.

Pour une vitesse d'injection de 50 m/min, les mesures sur produit composite extrait du bain permettent d'estimer la différence de hauteur entre les deux points de passage dans le bain de l'enveloppe tubulaire extérieure et de la paroi tubulaire intermédiaire à 50 à 60 cm. La valeur mesurée sur produit retiré du bain très rapidement après interruption de l'injection est en fait plus faible (38 cm) du fait que le calcium de la zone axiale continue à brûler à l'air libre pendant environ une minute.For an injection speed of 50 m / min, the measurements on composite product extracted from the bath make it possible to estimate the difference in height between the two points of passage in the bath of the outer tubular casing and of the intermediate tubular wall at 50 to 60 cm. The value measured on product removed from the bath very quickly after interruption of the injection is actually lower (38 cm) because the calcium in the axial zone continues to burn in the open air for about one minute.

L'étude du processus opératoire montre qu'une large part du calcium contenu dans la zone axiale a été libéré au voisinage du fond de la poche.The study of the operating process shows that a large part of the calcium contained in the axial zone has been released near the bottom of the pocket.

Ceci est mis en évidence notamment par l'aspect relativement calme des réactions dans le bain qui s'effectuent sans projection d'acier en dehors de la poche, quand on y injecte le fil selon l'invention ayant la composition ci-dessus décrite.This is highlighted in particular by the relatively calm appearance of the reactions in the bath which take place without steel being sprayed out of the pocket, when the wire according to the invention having the composition described above is injected into it.

De très nombreux modes de mise en oeuvre du produit et du procédé suivant l'invention peuvent être envisagés qui ne sortent pas du domaine de celle-ci.Many modes of implementation of the product and of the process according to the invention can be envisaged which do not depart from the field of the latter.

Claims (12)

1.) Composite formed body with metallic tubular casing of great length, inside which are accommodated pulverulent or granular material or materials used for the treatment of molten metal baths, into which this composite formed body is introduced, characterized in that it comprises, inside the tubular casing, an axial zone containing at least a first pulverulent or granular material surrounded by an intermediate metallic tubular wall, and an annular zone, contained between the intermediate tubular wall and the casing, containing also at least one second pulverulent or granular material.
2. Composite formed body according to claim 1, characterized in that the casing has a circular shape.
3. Composite formed body according to claims 1 or 2, characterized in that the casing is made of a metal whose melting point is at least equal to that of the metal of which the intermediate wall is made.
4. Composite formed body according to claim 3, characterized in that the casing and the intermediate wall are made of the same metal.
5. Composite formed body according to claim 3, characterized in that the casing and the intermediate wall are made of different metals.
6. Composite formed body according to one of claims 1 to 5, characterized in that at least the axial zone contains at least one element chosen from alloyed or, non-alloyed calcium and magnesium.
7. Composite formed body according to one of claims 1 to 5, characterized in that the second pulverulent or granular material has in total or in part the same composition as the first pulverulent or granular material.
8. Composite formed body according to one of claims 1 to 6, characterized in that the annular zone contains one or more materials chosen from MgO, CaO, CaCOs, Na2C03 and CaC2.
9. Process for treatment of molten metal baths by introduction into these baths of a composite formed body with metallic tubular casing of great length inside which are accommodated pulverulent or granular material or materials, characterized in that the composite formed body used comprises an axial zone surrounded by an intermediate metallic tubular wall and an annular zone contained between this wall and the casing, each of these zones containing at least one pulverulent or granular material and in that the axial zone contains, at least for the most part, the more volatile material or materials.
10. Process according to Claim 9, characterized in that in the case of desulphurization treatment of steels and cast irons the axial zone of the composite formed body used contains in the alloyed or non-alloyed state at least one metal of the group comprising magnesium and calcium.
11. Process according to claim 10, characterized in that the annular zone of the composite formed body used contains one or more materials ensuring a supplementary desulphurization, such as for example MgO, CaO, CaCOa, CaC2 and Na2C03.
12. Process according to claim 11, characterized in that the material or materials ensuring the supplementary desulphurization is or are associated with aluminium in granular or non-granular form.
EP88420033A 1987-02-03 1988-02-03 Composite product in a tubular envelope for treating molten-metal baths Expired - Lifetime EP0281485B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88420033T ATE57541T1 (en) 1987-02-03 1988-02-03 MIXED PRODUCT IN A TUBULAR SHELL FOR THE TREATMENT OF MOLTEN METAL BATHS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8701433A FR2610331A1 (en) 1987-02-03 1987-02-03 COMPOSITE TUBULAR ENVELOPE PRODUCT FOR PROCESSING FOUNDED METALLIC BATHS
FR8701433 1987-02-03

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EP0281485A1 EP0281485A1 (en) 1988-09-07
EP0281485B1 true EP0281485B1 (en) 1990-10-17

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US (1) US4863803A (en)
EP (1) EP0281485B1 (en)
JP (1) JPS63227712A (en)
KR (1) KR880010141A (en)
CN (1) CN1010324B (en)
AT (1) ATE57541T1 (en)
AU (1) AU607968B2 (en)
BR (1) BR8800405A (en)
DE (1) DE3860801D1 (en)
DK (1) DK52088A (en)
ES (1) ES2018355B3 (en)
FR (1) FR2610331A1 (en)
GR (1) GR3000950T3 (en)
IN (1) IN169055B (en)
ZA (1) ZA88736B (en)

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SE512574C2 (en) * 1998-08-25 2000-04-03 Partek Nordkalk Ab Elongated product that is effective in immersing in a molten steel bath for sulfur treatment
US6346135B1 (en) * 1998-12-10 2002-02-12 Minerals Technologies Inc. Cored wire for treating molten metal
US6770366B2 (en) * 2000-06-28 2004-08-03 Affival S.A. Cored wire for introducing additives into a molten metal bath
FR2821626B1 (en) * 2001-03-05 2004-05-07 Affival Sa FURNISHED WIRE FOR THE INTRODUCTION OF ADDITIVES INTO A FUSED METAL BATH
FR2871477B1 (en) 2004-06-10 2006-09-29 Affival Sa Sa WIRE FOURRE
CN1328394C (en) * 2005-07-16 2007-07-25 包头文鑫实业有限公司 Compound coate with with powder core and its making process
CN100381586C (en) * 2006-01-17 2008-04-16 沈阳东北大学冶金技术研究所 Cored wire for deoxidation of molten steel
WO2012027866A1 (en) * 2010-09-03 2012-03-08 安帝铁合金(天津)有限公司 Multi-layer cored wire
FR3018524B1 (en) * 2014-03-11 2017-03-10 Affival PROCESS FOR THE DESULFURATION OF A LIQUID IRON AND FILLED YARN FOR ITS IMPLEMENTATION
WO2017105280A1 (en) * 2015-12-14 2017-06-22 Александр Алексеевич НЕРЕТИН Composite cored wire
RU169359U1 (en) * 2015-12-14 2017-03-15 Александр Алексеевич Неретин Combined Injection Wire
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RU184357U9 (en) * 2017-08-11 2021-10-08 Арам Михайлович Караханянц Injection wire for the processing of metallurgical melts
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US4863803A (en) 1989-09-05
AU607968B2 (en) 1991-03-21
KR880010141A (en) 1988-10-07
GR3000950T3 (en) 1991-12-10
BR8800405A (en) 1988-09-20
DK52088A (en) 1988-08-04
IN169055B (en) 1991-08-24
FR2610331A1 (en) 1988-08-05
CN1010324B (en) 1990-11-07
AU1118788A (en) 1988-08-04
EP0281485A1 (en) 1988-09-07
ATE57541T1 (en) 1990-11-15
JPS63227712A (en) 1988-09-22
ZA88736B (en) 1988-08-03
DE3860801D1 (en) 1990-11-22
DK52088D0 (en) 1988-02-02
ES2018355B3 (en) 1991-04-01
CN88100499A (en) 1988-08-17

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