EP0190089B1 - Process for treating liquid metals by a calcium-containing cored wire - Google Patents
Process for treating liquid metals by a calcium-containing cored wire Download PDFInfo
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- EP0190089B1 EP0190089B1 EP86420021A EP86420021A EP0190089B1 EP 0190089 B1 EP0190089 B1 EP 0190089B1 EP 86420021 A EP86420021 A EP 86420021A EP 86420021 A EP86420021 A EP 86420021A EP 0190089 B1 EP0190089 B1 EP 0190089B1
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- alloy
- cored wire
- calcium
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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
- C21C7/0645—Agents used for dephosphorising or desulfurising
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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
- C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
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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
- C21C7/06—Deoxidising, e.g. killing
Definitions
- the process which is the subject of the invention relates to the treatment of liquid metals and in particular liquid steel by means of a cored wire whose core contains calcium.
- the term cored wire is used here to designate a product comprising a tubular metallic envelope of great length inside which is housed a material in divided or massive form. This cored wire allows this material to be introduced into a metallic bath, avoiding any contact with air or slag, that is to say with better efficiency and in a more reproducible manner.
- EP 34 994 describes a composite product with tubular casing and core in compacted pulverulent material which is used in particular for the treatment of liquid steel (page 8, lines 13-35).
- This cored wire comprises a thin steel casing and a pulverulent material core containing calcium.
- the rate of introduction of the latter into liquid steel must be limited to approximately 30 to 40 g per tonne of steel. liquid and per minute. As in practice, approximately 125 to 600 g of Ca are introduced per tonne of liquid steel in total, it can be seen that the treatment has a duration of 4 to 15 minutes.
- the thickness of the envelope of the cored wire and its internal section must be adjusted as a function of this speed of introduction so that this envelope does not dissolve prematurely before the cored wire has reached the bottom of the steel pocket liquid, the thickness of said envelope increasing when the speed of introduction decreases.
- the use of the Si-Ca alloy has the serious disadvantage of introducing about twice as much silicon into the steel as calcium.
- the Si-Ca alloy used in fact contains approximately 60% by mass of Si and experience has shown that it is hardly possible to significantly enrich this Ca alloy above 40%. While only about 15% of the Ca introduced into the steel remains fixed there, the Si, on the contrary, is completely fixed.
- the steel is therefore enriched with 250 to 1,200 p.p.m. of Si depending on the amount of Ca introduced included in the range of 125 to 600 g / t of liquid steel.
- the acceptable limit of Si content is of the order of 200 to 300 ppm is therefore not possible to respect it if an Si-Ca alloy is used as the core of a cored wire introduced into such a steel.
- European patent application 30 043 describes a method for treating liquid metals, in which a mixture of powders sheathed in a mild steel casing is introduced into the metal bath.
- This mixture comprises a component "A” consisting of reactive metals such as Mg, Ca, and rare earth metals, and a component “B” comprising Fe, Ni or Mn.
- component “A” consisting of reactive metals such as Mg, Ca, and rare earth metals
- component “B” comprising Fe, Ni or Mn.
- the presence of the metal particles of component “B” ensures the dispersion of the metallic vapors given off by metals such as Mg or Ca at high vapor pressure. This reduces the violence of the boiling of the metal bath and the importance of splashes of liquid metal.
- German patent 974 835 also proposes the deoxidation of cast irons and steels by reactive metals such as AI, Ca, Ti, Mg, Ce. These metals are introduced into the metal bath after a first deoxidation by a ferro alloy. The reactive metal is protected by a sheathing tube made of steel or metal or another alloy steel, according to the needs of metallurgy. No particular solution is proposed to the problem posed by the very high vapor pressure of metals such as Ca or Mg at the temperature of a bath of liquid steel.
- German patent 1 220 617 a treatment alloy is proposed which makes it possible to obtain fine grain steels.
- This alloy contains from 5 to 40% of Ca, 5 to 55% of one or more elements of the group comprising AI, Mn, Ni, Si, possibly small amounts of Ce, Li, Sr, Ba, Mg, the rest being Fe, at a content of 10 to 80%, which increases the density of the alloy so as to promote its penetration into the liquid steel to be treated.
- two treatment alloys are indicated: the first contains Fe 15.6%, Mn 12.7%, Ca 20.5%, Si 45.7%, Mg 4.5%. The second contains: Fe 33.5%, Ca 29.5%, Si 36%. It can be seen that these alloys have a relatively low content of highly reactive elements such as Ca and Mg. By cons they contain silicon at a high content which is unfavorable when this element is not desired.
- US Pat. No. 4,094,666 describes a method for refining cast irons and steels using Ca or Mg, with or without the addition of bastnaesite (Ce and La fluocarbonate) in a sheath of mild steel.
- bastnaesite Ca and Mg
- Ca and Mg reactive metals
- Bastnaesite Ca and La fluocarbonate
- the amounts of reactive metals (Ca and Mg) with or without added bastnaesite are between 0.3 and 0.5% of the mass of the steel or cast iron bath to be treated, ie 3 to 5 kg per tonne. So there are considerable losses.
- ferrous metals such as steels or cast iron in such a particularly effective manner, in particular with the aim of deoxidizing and / or desulfurizing them and / or modifying the nature and the morphology. inclusions.
- the process for treating metals or alloys in the liquid state, in particular ferrous metals, which is the subject of the invention makes it possible to solve the problem as a whole. It consists in preparing a metal or metallic alloy in the liquid state, preferably subjecting it, beforehand, to deoxidation, then in introducing into the metallic bath formed a cored wire comprising a metallic tubular envelope of great length and a core, the soul containing a material which is constituted for at least 30% by mass by an alloy whose calcium content is at least 75% by mass, an alloy also containing at least one metal from the group formed by nickel and aluminum the total content of this nickel plus aluminum alloy being at least equal to 5% by mass.
- the calcium content of the alloy is at least 80% by mass, the nickel content plus aluminum being in this case limited to 20% by mass.
- the alloy may in particular optionally contain up to 15% by mass of silicon and also optionally up to 2% by mass of magnesium.
- This alloy is preferably used in divided form, that is to say in powder form or even better preferably in granular form, the maximum grain size then being, preferably also, of the order of 2 mm.
- This alloy may be in the compacted state or not inside the cored wire.
- This material can also, for certain applications, contain another alloy comprising calcium, such as a silico-calcium. It may also contain elements or not, in alloyed or non-alloyed form, making it possible in particular to adjust the composition of the metal bath.
- it can contain elements or compounds, metallic or non-metallic, which contribute to the treatment of this metallic bath, in particular in cases where it is made of steel or of cast iron.
- the material which forms the core of the cored wire is an alloy, according to the composition given above and not a mixture.
- the speed of introduction of the cored wire containing the Ca alloy into the liquid steel is determined so that the amount of Ca introduced per minute is approximately 80 to 120 g. of Ca per tonne of liquid steel, the total amount of Ca introduced being from 125 to 600 g per tonne of liquid steel, the introduction being able to be carried out for example in a ladle and / or in a distributor in the case of a casting keep on going.
- the process according to the invention also applies to the preparation of steels having a particular aptitude for stamping.
- the silicon content of the liquid steel must then be limited to below 300 ppm before introduction of the cored wire, and the composition of the material forming the core thereof must be adjusted, from the silicon content point of view, so that the content of the liquid steel, after introduction of the cored wire, does not excessively exceed this content of 300 ppm.
- the invention also relates to a cored wire per putting to treat a metal or liquid alloy in particular a steel whose core contains a material preferably in divided form, that is to say pulverulent or granular, compacted or not, which is constituted for at least 30% by mass by a alloy containing at least 75% by mass of calcium alloyed with at least one metal of the group formed from nickel and aluminum, the total content of this alloy of nickel plus aluminum being at least equal to 5% by mass.
- Figure 2 shows the ends such as (7) of the fixing rods (6) of the cups which pass through the disc to which they are attached in a distribution as regular as possible.
- a device (8) shown schematically comprises rollers (9) which penetrate from top to bottom, substantially vertically, a cored wire (10) in the liquid steel.
- FIG. 1 shows in diagram form the results obtained. 41 steel castings are tested. Each of these flows weighing 83 tonnes is placed in the pocket (1) of FIG. 1 and then treated with the cored wire (10).
- This cored wire has a mild steel casing 0.4 mm thick and a rectangular section of 16 by 7.5 mm.
- the core of this cored wire is a divided material consisting of a CaNi alloy containing 87% by mass of Ca and 11% by mass of Ni.
- the weight per meter of alloy contained in the cored wire is 110 g or 95.7 g of Ca.
- the line marked (L) in FIG. 3 separates a lower zone for which, out of 19 tests, only 1 results in too intense bubbling, with an upper zone for which, in 22 tests 9, causes too intense bubbling.
- This line (L) corresponds to a speed of introduction of the cored wire of 105 m / min, which corresponds for a mass of liquid steel of 83 t to 120 g of Ca / t / min.
- a series of tests, similar to those carried out using a Ca Ni alloy, are then carried out using a Ca AI alloy containing 93% by mass of calcium and 5% by mass of aluminum. This alloy is in the divided state, like the Ca Ni alloy which has just been mentioned.
- the analyzes carried out show that the calcium introduction yield is, in the case of the Si Ca alloy, on average 15%.
- the silicon introduction yield is practically 100%.
- 360 ppm of silicon is fixed.
- Such an addition is incompatible with the production of a steel for deep drawing, for which the silicon content must be less than 300 ppm and even, in certain cases, less than 200 ppm.
- the invention can also be used, by way of another example, by using a cored wire comprising, as material constituting the core, respectively 50% by mass of Ca-Ni alloy at 90% Ca and 8% Ni and 50% by mass of Ca-Si alloy at 30% Ca and 60% Si.
- a cored wire comprising, as material constituting the core, respectively 50% by mass of Ca-Ni alloy at 90% Ca and 8% Ni and 50% by mass of Ca-Si alloy at 30% Ca and 60% Si.
- Such a mixture contains 60% Ca and 30% silicon by weight.
- the mass of product to be added with the cored wire above containing 60% Ca is twice less than that to be added with a cored wire containing Ca Si containing 30% Ca and 60% Si.
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- Chemical Treatment Of Metals (AREA)
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Abstract
Description
Le procédé qui fait l'objet de l'invention concerne le traitement de métaux liquides et notamment d'acier liquide au moyen d'un fil fourré dont l'âme contient du calcium. Le terme fil fourré est utilisé ici pour désigner un produit comportant une enveloppe métallique tubulaire de grande longueur à l'intérieur de laquelle est logée une matière sous forme divisée ou massive. Ce fil fourré permet d'introduire cette matière au sein d'un bain métallique en évitant tout contact avec l'air ou le laitier, c'est-à-dire avec un meilleur rendement et de façon plus reproductible.The process which is the subject of the invention relates to the treatment of liquid metals and in particular liquid steel by means of a cored wire whose core contains calcium. The term cored wire is used here to designate a product comprising a tubular metallic envelope of great length inside which is housed a material in divided or massive form. This cored wire allows this material to be introduced into a metallic bath, avoiding any contact with air or slag, that is to say with better efficiency and in a more reproducible manner.
Un tel mode de traitement de bains métalliques est bien connu. Ainsi la demande de brevet européen EP 34 994 décrit un produit composite à enveloppe tubulaire et âme en matière pulvérulente compactée qui est utilisé en particulier pour le traitement de l'acier liquide (page 8, lignes 13-35). Ce fil fourré comporte une enveloppe de faible épaisseur en acier et une âme en matière pulvérulente contenant du calcium.Such a method of treating metal baths is well known. Thus, European patent application EP 34 994 describes a composite product with tubular casing and core in compacted pulverulent material which is used in particular for the treatment of liquid steel (page 8, lines 13-35). This cored wire comprises a thin steel casing and a pulverulent material core containing calcium.
L'utilisation du calcium comme composant de l'âme de fils fourrés, utilisés pour le traitement de l'acier liquide, a pris un développement important dans ces dernières années. En effet, le calcium permet de réduire la teneur en oxygène soluble de l'acier et favorise parallèlement sa désulfuration. Il permet aussi de modifier la nature et la morphologie des inclusions, telles que celles d'alumine, qui sonttrasn- formées en aluminates de chaux liquides. On évite ainsi l'obturation des busettes de coulée, phénomène particulièrement gênant pour la coulée continue et aussi la formation au cours du corroyage à chaud de lignes d'inclusions allongées qui réduisent la ductilité en travers des produits obtenus. Enfin, ces inclusions modifiées sont moins abrasives vis- à-vis des outils de coupe pour usinage à grande vitesse.The use of calcium as a component of the core of cored wires, used for the treatment of liquid steel, has taken an important development in recent years. Indeed, calcium makes it possible to reduce the soluble oxygen content of the steel and at the same time promotes its desulfurization. It also makes it possible to modify the nature and the morphology of inclusions, such as those of alumina, which are formed into aluminates of liquid lime. This prevents plugging of the casting nozzles, a particularly troublesome phenomenon for continuous casting and also the formation during hot working of elongated inclusion lines which reduce the ductility across the products obtained. Finally, these modified inclusions are less abrasive with respect to cutting tools for high speed machining.
Grâce au fil fourré, on introduit sans difficultés le calcium au fond d'une poche remplie d'acier liquide au sein duquel il peut ainsi réagir de façon particulièrement efficace. Mais on n'évite pas le violent bouillonnement de cet acier provoqué par la brusque volatilisation de ce calcium. Sa tension de vapeur est en effet d'environ 1,8 atm à 1600°C. Ce bouillonnement, s'il est trop intense, peut perturber les conditions de pénétration du fil fourré dans le bain d'acier. En même temps, des projections d'acier liquide se produisent qui traversent la couche de laitier et s'oxydent au contact de l'air avant de retomber. On constate alors une remontée des teneurs en 02, N2 et même H2 de l'acier obtenu.Thanks to the cored wire, calcium is easily introduced into the bottom of a pocket filled with liquid steel, within which it can thus react particularly effectively. But we do not avoid the violent bubbling of this steel caused by the sudden volatilization of this calcium. Its vapor pressure is indeed about 1.8 atm at 1600 ° C. This boiling, if it is too intense, can disturb the conditions of penetration of the cored wire into the steel bath. At the same time, splashes of liquid steel occur which pass through the slag layer and oxidize on contact with the air before falling. There is then a rise in the contents of 02, N2 and even H2 of the steel obtained.
L'expérience a montré que si on utilise comme âme du fil fourré une matière contenant du calcium non allié, il faut limiter la vitesse d'introduction de celui-ci dans l'acier liquide à environ 30 à 40 g par tonne d'acier liquide et par minute. Comme dans la pratique on introduit environ 125 à 600 g de Ca par tonne d'acier liquide au total, on voit que le traitement a une durée de 4 à 15 minutes.Experience has shown that if a core material containing unalloyed calcium is used as the core of the cored wire, the rate of introduction of the latter into liquid steel must be limited to approximately 30 to 40 g per tonne of steel. liquid and per minute. As in practice, approximately 125 to 600 g of Ca are introduced per tonne of liquid steel in total, it can be seen that the treatment has a duration of 4 to 15 minutes.
L'épaisseur de l'enveloppe du fil fourré et sa section intérieure doivent être ajustées en fonction de cette vitesse d'introduction de façon que cette enveloppe ne se dissolve pas prématurément avant que le fil fourré ait atteint le fond de la poche d'acier liquide, l'épaisseur de ladite enveloppe croissant quand la vitesse d'introduction diminue.The thickness of the envelope of the cored wire and its internal section must be adjusted as a function of this speed of introduction so that this envelope does not dissolve prematurely before the cored wire has reached the bottom of the steel pocket liquid, the thickness of said envelope increasing when the speed of introduction decreases.
De nombreuses méthodes ont été proposées en vue de traiter des métaux ou alliages liquides, et en particulier des fontes et des aciers, par du calcium ou d'autres éléments ou composés fortement réactifs. De nombreuses compositions comportant du calcium ou d'autres éléments, souvent sous forme de mélanges ou d'alliages, ont également été proposées en vue de leur utilisation dans de telles méthodes.Numerous methods have been proposed with a view to treating metals or liquid alloys, and in particular cast irons and steels, with calcium or other highly reactive elements or compounds. Many compositions comprising calcium or other elements, often in the form of mixtures or alloys, have also been proposed with a view to their use in such methods.
Ainsi dans la demande de brevet européen 34 994, on décrit un moyen d'introduction de Ca en fil fourré qui consiste à faire appel à un alliage Si-Ca contenant environ 30% de Ca en masse. On constate alors que le bouillonnement de l'acier liquide est réduit et on peut, de cette façon, introduire en fil fourré du calcium sous forme de Si-Ca, dans l'acier liquide, à une vitesse correspondant à environ 80 grammes par tonne d'acier liquide à la minute sans bouillonnement excessif. On multiplie ainsi environ par 2 la vitesse d'introduction du calcium.Thus, in European patent application 34 994, a means of introducing Ca in a cored wire is described which consists in using an Si-Ca alloy containing approximately 30% of Ca by mass. It is then observed that the boiling of the liquid steel is reduced and it is possible, in this way, to introduce calcium-filled wire in the form of Si-Ca into the liquid steel, at a speed corresponding to approximately 80 grams per tonne liquid steel per minute without excessive bubbling. The rate of introduction of calcium is thus multiplied by about 2.
L'utilisation de l'alliage Si-Ca présente le sérieux inconvénient d'introduire dans l'acier environ 2 fois plus de silicium que de calcium. L'alliage Si-Ca utilisé contient en effet environ 60% en masse de Si et l'expérience a montré qu'il n'est guère possible d'enrichir notablement cet alliage en Ca au-dela de 40%. Alors que environ 15% seulement du Ca introduit dans l'acier y reste fixé, le Si au contraire est fixé intégralement. On enrichit donc l'acier de 250 à 1200 p.p.m. de Si suivant la quantité de Ca introduite comprise dans la fourchette de 125 à 600 g/t d'acier liquide. Pour de nombreuses applications, une telle addition de Si est très défavorable en particulier pour le traitement des aciers utilisés pour l'emboutissage profond. Pour de tels aciers, la limite acceptable de teneur en Si est de l'ordre de 200 à 300 p.p.m. n'est donc pas possible de la respecter si on utilise un alliage Si-Ca comme âme d'un fil fourré introduit dans un tel acier.The use of the Si-Ca alloy has the serious disadvantage of introducing about twice as much silicon into the steel as calcium. The Si-Ca alloy used in fact contains approximately 60% by mass of Si and experience has shown that it is hardly possible to significantly enrich this Ca alloy above 40%. While only about 15% of the Ca introduced into the steel remains fixed there, the Si, on the contrary, is completely fixed. The steel is therefore enriched with 250 to 1,200 p.p.m. of Si depending on the amount of Ca introduced included in the range of 125 to 600 g / t of liquid steel. For many applications, such an addition of Si is very unfavorable in particular for the treatment of steels used for deep drawing. For such steels, the acceptable limit of Si content is of the order of 200 to 300 ppm is therefore not possible to respect it if an Si-Ca alloy is used as the core of a cored wire introduced into such a steel.
La demande de brevet européen 30 043 décrit un procédé de traitement de métaux liquides, dans lequel on introduit dans le bain métallique un mélange de poudres gainé dans une enveloppe en acier doux. Ce mélange comporte un composant «A» constitué par des métaux réactifs tels que Mg, Ca, et des métaux des terres rares, et un composant «B» comprenant Fe, Ni ou Mn. Les meilleurs résultats sont obtenus avec des mélanges comprenant des quantités sensiblement égales de chacun des deux composants. La présence des particules des métaux du composant «B» assure le dispersion des vapeurs métalliques dégagées par les métaux tels que Mg ou Ca à forte tension de vapeur. On réduit ainsi la violence du bouillonnement du bain métallique et l'importance des projections de métal liquide. Cependant la nécessité de loger dans l'enveloppe du fil fourré une âme comportant une quantité importante de composant «B», pratiquement inerte, accroît le coût du traitement et en prolonge la durée. De plus la différence de densité des deux composants peut provoquer une séparation de ceux-ci au cours de la mise en oeuvre du mélange et réduire l'efficacité de celui-ci.European patent application 30 043 describes a method for treating liquid metals, in which a mixture of powders sheathed in a mild steel casing is introduced into the metal bath. This mixture comprises a component "A" consisting of reactive metals such as Mg, Ca, and rare earth metals, and a component "B" comprising Fe, Ni or Mn. The best results are obtained with mixtures comprising substantially equal amounts of each of the two components. The presence of the metal particles of component “B” ensures the dispersion of the metallic vapors given off by metals such as Mg or Ca at high vapor pressure. This reduces the violence of the boiling of the metal bath and the importance of splashes of liquid metal. However, the need to accommodate in the envelope of the cored wire a core comprising a large quantity of component “B”, practically inert, increases the cost of the treatment and prolongs its duration. In addition, the difference in density of the two components can cause them to separate at the same time. during the implementation of the mixture and reduce the effectiveness thereof.
Le brevet allemand 974 835 propose également la désoxydation des fontes et des aciers par des métaux réactifs tels que AI, Ca, Ti, Mg, Ce. On introduit ces métaux dans le bain métallique après une première désoxydation par un ferro alliage. On protège le métal réactif par un tube de gainage en acier ou en métal ou en un autre acier allié, suivant les besoins de la métallurgie. Il n'est pas proposé de solution particulière au problème posé par la tension de vapeur très élevée de métaux tels que Ca ou Mg à la température d'un bain d'acier liquide.German patent 974 835 also proposes the deoxidation of cast irons and steels by reactive metals such as AI, Ca, Ti, Mg, Ce. These metals are introduced into the metal bath after a first deoxidation by a ferro alloy. The reactive metal is protected by a sheathing tube made of steel or metal or another alloy steel, according to the needs of metallurgy. No particular solution is proposed to the problem posed by the very high vapor pressure of metals such as Ca or Mg at the temperature of a bath of liquid steel.
Dans le brevet allemand 1 220 617 il est proposé un alliage de traitement qui permet d'obtenir des aciers à grains fins. Cet alliage contient de 5 à 40% de Ca, 5 à 55% d'un ou plusieurs éléments du groupe comprenant AI, Mn, Ni, Si, éventuellement de petites quantités de Ce, Li, Sr, Ba, Mg, le reste étant Fe, à une teneur de 10 à 80%, qui accroît la densité de l'alliage de façon à favoriser sa pénétration dans l'acier liquide à traiter. On indique à titre d'exemple deux alliages de traitement: le premier contient Fe 15,6%, Mn 12,7%, Ca 20,5%, Si 45,7%, Mg 4,5%. Le deuxième contient: Fe 33,5%, Ca 29,5%, Si 36%. On voit que ces alliages ont une relativement faible teneur en éléments fortement réactifs tels que Ca et Mg. Par contre ils contiennent du silicium à une teneur élevée ce qui est défavorable lorsque cet élément n'est pas souhaité.In
Le brevet US 4 094 666 décrit une méthode d'affinage des fontes et aciers au moyen de Ca ou de Mg, additionné ou non de bastnaesite (fluocarbonate de Ce et La) sous gaine d'acier doux. Comme indiqué plus haut le calcium et le magnésium ont l'un et l'autre une grande efficacité mais provoquent, à cause de leur très forte tension de vapeur, des projections violentes lors de leur introduction dans des bains métalliques. Les quantités de métaux réactifs (Ca et Mg) additionnés ou non de bastnaesite sont comprises entre 0,3 et 0,5% de la masse du bain d'acier ou de fonte à traiter soit 3 à 5 kg par tonne. Il y a donc des pertes considérables.US Pat. No. 4,094,666 describes a method for refining cast irons and steels using Ca or Mg, with or without the addition of bastnaesite (Ce and La fluocarbonate) in a sheath of mild steel. As indicated above, calcium and magnesium both have great efficiency but cause, due to their very high vapor pressure, violent projections when they are introduced into metal baths. The amounts of reactive metals (Ca and Mg) with or without added bastnaesite are between 0.3 and 0.5% of the mass of the steel or cast iron bath to be treated, ie 3 to 5 kg per tonne. So there are considerable losses.
On a recherché la possibilité de metre au point un procédé d'introduction de calcium, par fil fourré, dans un bain métallique, notamment dans un bain d'acier, permettant d'effectuer une telle introduction à vitesse élevée, sans provoquer de bouillonnements excessifs entraînant des projections importantes au dessus du niveau du métal liquide. On a recherché ainsi la possibilité d'éviter, au cours de cette introduction, de contaminer le métal liquidue par des éléments nuisibles à ses propriétés mécaniques ou autres, tels que le silicium par exemple. On a recherché également la possibilité d'obtenir un rendement d'introduction du calcium aussi élevé que possible de façon à réduire au minimum le coût du traitement. Dans un but d'économie on cherche aussi à réduire au minimum les quantités d'éléments éventuellement associés au calcium pour former l'âme du fil fourré, même si ces éléments n'ont pas d'effet nuisible sur le bain métallique, de façon à limiter au minimum le volume de fil fourré nécessaire à la mise en oeuvre du calcium.We looked for the possibility of developing a method for introducing calcium, by flux-cored wire, into a metal bath, in particular into a steel bath, making it possible to carry out such an introduction at high speed, without causing excessive bubbling. causing significant projections above the level of the liquid metal. We therefore sought the possibility of avoiding, during this introduction, of contaminating the molten metal with elements harmful to its mechanical or other properties, such as silicon for example. We have also sought the possibility of obtaining a yield for introducing calcium as high as possible so as to minimize the cost of treatment. In order to save money, we also seek to minimize the quantities of elements possibly associated with calcium to form the core of the cored wire, even if these elements have no harmful effect on the metal bath, so to minimize the volume of cored wire necessary for the use of calcium.
On a recherché enfin la possibilité de traiter par un tel procédé de façon particulièrement efficace des métaux ferreux tels que des aciers ou des fontes en particulier dans le but de les désoxyder et/ou de les désulfurer et/ou de modifier la nature et la morphologie des inclusions.Finally, we looked for the possibility of treating ferrous metals such as steels or cast iron in such a particularly effective manner, in particular with the aim of deoxidizing and / or desulfurizing them and / or modifying the nature and the morphology. inclusions.
Le procédé de traitement de métaux ou alliages à l'état liquide notamment de métaux ferreux qui fait l'objet de l'invention permet de résoudre dans son ensemble le problème ainsi posé. Il consiste à préparer un métal ou alliage métallique à l'état liquide, à lui faire subir, de préférence, au préalable, une désoxydation, puis à introduire dans le bain métallique formé un fil fourré comportant une enveloppe tubulaire métallique de grande longueur et une âme, l'âme contenant une matière qui est constituée pour au moins 30% en masse par un alliage dont la teneur en calcium est d'au moins 75% en masse, alliage contenant aussi au moins un métal du groupe formé du nickel et de l'aluminium la teneur totale de cet alliage en nickel plus aluminium étant au moins égale à 5% en masse. De préférence la teneur en calcium de l'alliage est d'au moins 80% en masse, la teneur en nickel pluis aluminium étant dans ce cas limitée à 20% en masse. L'alliage peut en particulier contenir de façon facultative jusqu'à 15% en masse de silicium et aussi de façon facultative jusqu'à 2% en masse de magnésium. Cet alliage est mis préférentiellement en oeuvre sous forme divisée c'est-à-dire sous forme pulvérulente ou encore mieux de préférence sous forme granulaire, la dimension maximum des grains étant alors, de préférence également, de l'ordre de 2 mm. Cet alliage peut se trouver à l'état compacté ou non à l'intérieur du fil fourré. Cette matière peut aussi pour certaines applications contenir un autre alliage comportant du calcium, tel qu'un silico-calcium. Elle peut contenir en plus des éléments ou non, sous forme alliée ou non-allièe, permettant notamment d'ajuster la composition du bain métallique. Elle peut enfin contenir des éléments ou composés, métalliques ou non métalliques, qui contribuent au traitement de ce bain métallique en particulier dans les cas où celui-ci est constitué par un acier ou par une fonte.The process for treating metals or alloys in the liquid state, in particular ferrous metals, which is the subject of the invention makes it possible to solve the problem as a whole. It consists in preparing a metal or metallic alloy in the liquid state, preferably subjecting it, beforehand, to deoxidation, then in introducing into the metallic bath formed a cored wire comprising a metallic tubular envelope of great length and a core, the soul containing a material which is constituted for at least 30% by mass by an alloy whose calcium content is at least 75% by mass, an alloy also containing at least one metal from the group formed by nickel and aluminum the total content of this nickel plus aluminum alloy being at least equal to 5% by mass. Preferably the calcium content of the alloy is at least 80% by mass, the nickel content plus aluminum being in this case limited to 20% by mass. The alloy may in particular optionally contain up to 15% by mass of silicon and also optionally up to 2% by mass of magnesium. This alloy is preferably used in divided form, that is to say in powder form or even better preferably in granular form, the maximum grain size then being, preferably also, of the order of 2 mm. This alloy may be in the compacted state or not inside the cored wire. This material can also, for certain applications, contain another alloy comprising calcium, such as a silico-calcium. It may also contain elements or not, in alloyed or non-alloyed form, making it possible in particular to adjust the composition of the metal bath. Finally, it can contain elements or compounds, metallic or non-metallic, which contribute to the treatment of this metallic bath, in particular in cases where it is made of steel or of cast iron.
On insiste sur le fait que la matière qui forme l'âme du fil fourré est un alliage, selon la composition donnée ci-dessus et non un mélange.It is emphasized that the material which forms the core of the cored wire is an alloy, according to the composition given above and not a mixture.
De préférence également, dans le cas de l'acier la vitesse d'introduction du fil fourré contenant l'alliage de Ca dans l'acier liquide est déterminée de façon que la quantité de Ca introduite par minute soit d'environ 80 à 120 g de Ca par tonne d'acier liquide, la quantité totale de Ca introduite étant de 125 à 600 g par tonne d'acier liquide, l'introduction pouvant se faire par exemple en poche et/ou en répartiteur dans le cas d'une coulée continue.Preferably also, in the case of steel, the speed of introduction of the cored wire containing the Ca alloy into the liquid steel is determined so that the amount of Ca introduced per minute is approximately 80 to 120 g. of Ca per tonne of liquid steel, the total amount of Ca introduced being from 125 to 600 g per tonne of liquid steel, the introduction being able to be carried out for example in a ladle and / or in a distributor in the case of a casting keep on going.
Le procédé suivant l'invention s'applique également à la préparation d'aciers ayant une aptitude particulière à l'emboutissage. La teneur en silicium de l'acier liquide doit alors être limitée au dessous de 300 ppm avant introduction du fil fourré, et la composition de la matière formant l'âme de celui-ci doit être ajustée, du point de vue teneur en silicium, de façon que la teneur de l'acier liquide, après introduction du fil fourré, ne dépasse pas de façon trop notable cette teneur de 300 ppm.The process according to the invention also applies to the preparation of steels having a particular aptitude for stamping. The silicon content of the liquid steel must then be limited to below 300 ppm before introduction of the cored wire, and the composition of the material forming the core thereof must be adjusted, from the silicon content point of view, so that the content of the liquid steel, after introduction of the cored wire, does not excessively exceed this content of 300 ppm.
L'invention concerne également un fil fourré permettant de traiter un métal ou alliage liquide notamment un acier dont l'âme contient une matière préférentiellement sous forme divisée, c'est-à-dire pulvérulente ou granulaire, compactée ou non, qui est constituée pour au moins 30% en masse par un alliage contenant au moins 75% en masse de calcium allié à au moins un métal du groupe formé du nickel et de t'atuminium, la teneur totale de cet alliage en nickel plus aluminium étant au moins égale à 5% en masse. Certaines autres caractéristiques intéressantes du fil fourré suivant l'invention ont déja été données à propos de la description du procédé et ne sont pas reprises ici.The invention also relates to a cored wire per putting to treat a metal or liquid alloy in particular a steel whose core contains a material preferably in divided form, that is to say pulverulent or granular, compacted or not, which is constituted for at least 30% by mass by a alloy containing at least 75% by mass of calcium alloyed with at least one metal of the group formed from nickel and aluminum, the total content of this alloy of nickel plus aluminum being at least equal to 5% by mass. Certain other interesting characteristics of the cored wire according to the invention have already been given in connection with the description of the process and are not repeated here.
La description et les figures ci-après présentent, de façon non limitative, un mode de mise en oeuvre de l'invention.
- La figure 1 est un schéma d'un dispositif permettant d'évaluer l'intensité du bouillonnement de l'acier liquide provoqué par l'introduction d'un fil fourré contenant du calcium.
- La figure 2 est un détail de la figure 1 vu suivant la flèche (F).
- La figure 3 est un diagramme qui montre le relation entre le vitesse d'introduction du fil fourré et l'intensité du bouillonnement de l'acier liquide.
- La figure 1 représente une poche ( 1 ) contenant 83t d'acier liquide (2). Cet acier non allié qui a subi une désoxydation préalable contient C=0,12% et Mn = 0,6%. Il est recouvert d'une couche de laitier (3). A une distance (H) de 300 mm de la surface du laitier se trouvent 16 coupelles, telles que (4), en acier, d'environ 50 mm de diamètre suspendues au-dessous d'un disque en acier (5)
de 1,2 m de diamètre lui-même suspendu au-dessus de la poche.
- Figure 1 is a diagram of a device for evaluating the intensity of the boiling of liquid steel caused by the introduction of a cored wire containing calcium.
- Figure 2 is a detail of Figure 1 seen along the arrow (F).
- FIG. 3 is a diagram which shows the relationship between the speed of introduction of the cored wire and the intensity of the boiling of the liquid steel.
- FIG. 1 represents a pocket (1) containing 83 tonnes of liquid steel (2). This unalloyed steel which has undergone prior deoxidation contains C = 0.12% and Mn = 0.6%. It is covered with a layer of slag (3). At a distance (H) of 300 mm from the slag surface are 16 cups, such as (4), made of steel, of about 50 mm in diameter suspended below a steel disc (5) of 1 , 2 m in diameter itself suspended above the pocket.
On voit figure 2 les extrémités telles que (7) des tiges de fixation (6) des coupelles qui traversent le disque auquel elles sont accrochées suivant une répartition aussi régulière que possible. Sur la droite de la figure 1, un dispositif (8) présenté de façon schématique comporte des rouleaux (9) qui font pénétrer de haut en bas, de façon sensiblement verticale, un fil fourré (10) dans l'acier liquide.Figure 2 shows the ends such as (7) of the fixing rods (6) of the cups which pass through the disc to which they are attached in a distribution as regular as possible. On the right of Figure 1, a device (8) shown schematically comprises rollers (9) which penetrate from top to bottom, substantially vertically, a cored wire (10) in the liquid steel.
Des essais préliminaires ont montré que l'intensité du bouillonnement du métal liquide, provoqué par l'introduction du fil fourré, ne devait pas êtretelle que plus de la moitié des coupelles (4) reçoive des projections de métal et/ou de laitier. Ces essais préliminaires ont montré également que, dans le cas d'un fil fourré dont l'âme est du calcium divisé non allié, cette intensité de bouillonnement est atteinte pour une vitesse d'introduction correspondant à 40 g de Ca par tonne d'acier liquide et par minute.Preliminary tests have shown that the intensity of the boiling of the liquid metal, caused by the introduction of the cored wire, should not be such that more than half of the cups (4) receive splashes of metal and / or slag. These preliminary tests also showed that, in the case of a cored wire whose core is unalloyed divided calcium, this boiling intensity is reached for an introduction speed corresponding to 40 g of Ca per tonne of steel liquid and per minute.
Des essais systématiques sont alors effectués sur des coulées d'un four à arc élaborant un acier du type A42, non allié, contenant C=0,12% et Mn=0,6%. La figure 3 montre sous forme de diagramme les résultats obtenus. 41 coulées d'acier sont testées. Chacune de ces coulées d'un poids de 83t est mise en place dans la poche (1) de la figure 1 puis traitée par le fil fourré (10). Ce fil fourré a une enveloppe en acier doux de 0,4 mm d'épaisseur et une section rectangulaire de 16 par 7,5 mm. L'âme de ce fil fourré est une matière divisée constituée d'un alliage CaNi contenant 87% en masse de Ca et 11 % en masse de Ni. Le poids au mètre d'alliage contenu dans le fil fourré est de 110 g soit 95,7 g de Ca. On voit sur la figure 3 en ordonnée les vitesses d'introduction de fil fourré en m/min. En abscisse sont données les températures de l'acier liquide. Le résultat de chaque essai est représenté par une croix (x) ou un rond (o). La croix (x) correspond à un bouillonnement trop intense de l'acier liquide dont les projections d'acier et de laitier ont atteint plus de 8 coupelles (4). Le rond (o) correspond à un bouillonnement acceptable pour lequel pas plus de 8 coupelles ont été atteintes.Systematic tests are then carried out on castings from an arc furnace developing a steel of type A42, unalloyed, containing C = 0.12% and Mn = 0.6%. Figure 3 shows in diagram form the results obtained. 41 steel castings are tested. Each of these flows weighing 83 tonnes is placed in the pocket (1) of FIG. 1 and then treated with the cored wire (10). This cored wire has a mild steel casing 0.4 mm thick and a rectangular section of 16 by 7.5 mm. The core of this cored wire is a divided material consisting of a CaNi alloy containing 87% by mass of Ca and 11% by mass of Ni. The weight per meter of alloy contained in the cored wire is 110 g or 95.7 g of Ca. We see in Figure 3 on the ordinate the velocities of introduction of cored wire in m / min. On the abscissa are given the temperatures of the liquid steel. The result of each test is represented by a cross (x) or a circle (o). The cross (x) corresponds to an excessively intense bubbling of the liquid steel whose projections of steel and slag have reached more than 8 cups (4). The circle (o) corresponds to an acceptable bubbling for which no more than 8 cups have been reached.
On voit que la ligne repérée (L) sur la figure 3 sépare une zone inférieure pour laquelle, sur 19 essais, 1 seulement entraîne un bouillonnement trop intense, d'avec une zone supérieure pour laquelle sur 22 essais 9 entraînent un bouillonnement trop intense. Cette ligne (L) correspond à une vitesse d'introduction du fil fourré de 105 m/min, ce qui correspond pour une masse d'acier liquide de 83 t à 120 g de Ca/t/min. Une série d'essais, semblables à ceux effectués au moyen d'un alliage Ca Ni, sont ensuite effectués au moyen d'un alliage Ca AI contenant 93% en masse de calcium et 5% en masse d'aluminium. Cet alliage est à l'état divisé, comme l'alliage Ca Ni qui vient d'être cité. Ces essais montrent qu'il est possible de constituer avec cet alliage Ca AI l'âme dun fil fourré ayant des caractéristiques dimensionnelles très voisines de celles du fil mis en oeuvre dans le cas de l'alliage Ca Ni. Au cours de ces essais on constate que, comme dans le cas de l'alliage Ca Ni, il est possible d'introduire le fil fourré, ayant pour âme l'alliage Ca AI dont la composition vient d'être donnée, dans un bain d'acier liquide du type A42, contenant 83 t d'acier, à une vitesse correspondant à l'introduction d'environ 120 g de calcium par tonne d'acier liquide à la minute. Dans ces conditions on n'observe pas de projections importantes d'acier liquide.It can be seen that the line marked (L) in FIG. 3 separates a lower zone for which, out of 19 tests, only 1 results in too intense bubbling, with an upper zone for which, in 22 tests 9, causes too intense bubbling. This line (L) corresponds to a speed of introduction of the cored wire of 105 m / min, which corresponds for a mass of liquid steel of 83 t to 120 g of Ca / t / min. A series of tests, similar to those carried out using a Ca Ni alloy, are then carried out using a Ca AI alloy containing 93% by mass of calcium and 5% by mass of aluminum. This alloy is in the divided state, like the Ca Ni alloy which has just been mentioned. These tests show that it is possible to form with this Ca AI alloy the core of a cored wire having dimensional characteristics very close to those of the wire used in the case of the Ca Ni alloy. During these tests, it can be seen that, as in the case of the Ca Ni alloy, it is possible to introduce the cored wire, having the Ca Al alloy whose composition has just been given, in a bath. liquid steel of type A42, containing 83 tonnes of steel, at a rate corresponding to the introduction of approximately 120 g of calcium per tonne of liquid steel per minute. Under these conditions, no significant projections of liquid steel are observed.
Afin de comparer les rendements d'introduction du calcium dans le bain d'acier liquide c'est-à-dire le rapport exprimé en % en masse entre la quantité de calcium retenue dans le bain d'acier liquide et celle introduite au moyen du fil fourré, on traite dans les mêmes conditions opératoires des bains d'acier, contenant chacun 83 tonnes d'acier A42 soit par l'alliage Ca Ni soit par l'alliage Ca AI décrits plus haut. Dans chaque cas la quantité totale de calcium introduite est de 180 g partonne soit 0,0180% en masse. Les analyses effectuées montrent que les quantités de calcium retenues dans l'acier liquide en répartiteur sont en moyenne de 0,0034% dans le cas de l'alliage Ca Ni et de 0,0039% dans le cas de l'alliage Ca AI. Le rendement en calcium est donc de 19% avec l'alliage Ca Ni et 22% avec l'alliage Ca AI.In order to compare the yields of introduction of calcium into the liquid steel bath, that is to say the ratio expressed in% by mass between the quantity of calcium retained in the liquid steel bath and that introduced by means of the flux cored wire, steel baths are treated under the same operating conditions, each containing 83 tonnes of A42 steel either by the Ca Ni alloy or by the Ca AI alloy described above. In each case the total amount of calcium introduced is 180 g per unit, ie 0.0180% by mass. The analyzes carried out show that the amounts of calcium retained in the liquid steel in the distributor are on average 0.0034% in the case of the Ca Ni alloy and 0.0039% in the case of the Ca AI alloy. The calcium yield is therefore 19% with the Ca Ni alloy and 22% with the Ca AI alloy.
Au cours de ces mêmes essais, on a déterminé également la variation de la teneur en soufre du bain d'acier consécutive à l'introduction du calcium. On a constaté que cette teneur diminue, en moyenne, de 24% dans le cas de l'introduction de l'alliage Ca Ni et de 26% dans celui de l'introduction de l'alliage Ca AI.During these same tests, the variation in the sulfur content of the steel bath following the introduction of calcium was also determined. It has been found that this content decreases, on average, by 24% in the case of the introduction of the Ca Ni alloy and by 26% in that of the introduction of the Ca AI alloy.
A titre de comparation, on traite de la même façon 52 coulées d'un même acier au moyen d'un fil fourré, de mêmes caractéristiques, dont l'âme est constituée par un alliage Si Ca contenant en masse 60% de Si et 30% de Ca.By way of comparison, 52 castings of the same steel are treated in the same way by means of a cored wire, with the same characteristics, the core of which is constituted by an Si Ca alloy containing by
En établissant un diagramme semblable à celui de la figure 3, on constate qu'on peut tracer une ligne de séparation entre une zone inférieure pour laquelle la grande majorité des résultats ne donnent pas lieu à bouillonnement trop intense et une zone supérieure pour laquelle ce bouillonnement devient trop violent. Cette ligne de séparation correspond à une vitesse d'introduction du fil fourré de 120 m/min. Ce fil contenant 180 g d'alliage Si Ca au mètre, la vitesse maximale d'introduction du Ca est donc dans ce cas de 78 g par tonne à la minute.By establishing a diagram similar to that of FIG. 3, it can be seen that a dividing line can be drawn between a lower zone for which the vast majority of the results do not give rise to too intense bubbling and an upper zone for which this bubbling becomes too violent. This separation line corresponds to a speed of introduction of the cored wire of 120 m / min. This wire containing 180 g of Si Ca alloy per meter, the maximum speed of Ca introduction is therefore in this case 78 g per ton per minute.
Les analyses effectuées montrent que le rendement d'introduction du calcium est, dans le cas de l'alliage Si Ca de 15% en moyenne. Le rendement d'introduction du silicium est pratiquement de 100%. On voit que, déjà pour une introduction de 180 g de calcium par tonne d'acier liquide, on fixe 360 ppm de silicium. Une telle addition est incompatible avec l'élaboration d'un acier pour emboutissage profond, pour lequel la teneur en silicium doit être inférieure à 300 ppm et même, dans certains cas, inférieure à 200 ppm.The analyzes carried out show that the calcium introduction yield is, in the case of the Si Ca alloy, on average 15%. The silicon introduction yield is practically 100%. We see that, already for an introduction of 180 g of calcium per tonne of liquid steel, 360 ppm of silicon is fixed. Such an addition is incompatible with the production of a steel for deep drawing, for which the silicon content must be less than 300 ppm and even, in certain cases, less than 200 ppm.
On peut aussi exploiter l'invention, à titre d'autre exemple, en utilisant un fil fourré comprenant, comme matière constitutive de l'âme, respectivement 50% en masse d'alliage Ca-Ni à 90% Ca et 8% Ni et 50% en masse d'alliage Ca-Si à 30% Ca et 60% Si. Un tel mélange contient 60% de Ca et 30% de silicium en poids.The invention can also be used, by way of another example, by using a cored wire comprising, as material constituting the core, respectively 50% by mass of Ca-Ni alloy at 90% Ca and 8% Ni and 50% by mass of Ca-Si alloy at 30% Ca and 60% Si. Such a mixture contains 60% Ca and 30% silicon by weight.
Pour introduire la même quantité de calcium dans le bain, la masse de produit à ajouter avec le fil fourré ci-dessus contenant 60% de Ca est deux fois moindre que celle à ajouter avec un fil fourré contenant du Ca Si à 30% de Ca et 60% de Si.To introduce the same amount of calcium into the bath, the mass of product to be added with the cored wire above containing 60% Ca is twice less than that to be added with a cored wire containing Ca Si containing 30% Ca and 60% Si.
Par ailleurs, l'introduction de silicium est elle-même divisée par quatre.Furthermore, the introduction of silicon is itself divided by four.
Claims (18)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86420021T ATE40154T1 (en) | 1985-01-24 | 1986-01-22 | METHOD OF TREATMENT OF LIQUID METALS USING A CALCIUM-CONTAINING CORRED WIRE. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8501332 | 1985-01-24 | ||
| FR8501331A FR2576320B1 (en) | 1985-01-24 | 1985-01-24 | PROCESS FOR TREATING LIQUID FERROUS METALS BY FURNISHED CALCIUM-CONTAINING WIRE |
| FR8501331 | 1985-01-24 | ||
| FR8501332 | 1985-01-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0190089A1 EP0190089A1 (en) | 1986-08-06 |
| EP0190089B1 true EP0190089B1 (en) | 1989-01-18 |
Family
ID=26224355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86420021A Expired EP0190089B1 (en) | 1985-01-24 | 1986-01-22 | Process for treating liquid metals by a calcium-containing cored wire |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0190089B1 (en) |
| AT (1) | ATE40154T1 (en) |
| AU (1) | AU587228B2 (en) |
| DE (1) | DE3661841D1 (en) |
| ES (1) | ES8801386A1 (en) |
| WO (1) | WO1986004359A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| RU2152834C1 (en) * | 1999-12-06 | 2000-07-20 | Неретин Александр Алексеевич | Method for making calcium wire |
| EP1715065A3 (en) * | 2005-04-20 | 2007-08-15 | Corus Staal BV | A cored-wire for injecting into a steel melt and process of treating a steel melt using said wire |
| CN101906506A (en) * | 2010-08-19 | 2010-12-08 | 谢应凯 | Steel-covered aluminum-calcium alloy for steelmaking and preparation method thereof |
| RU2443785C1 (en) * | 2010-09-27 | 2012-02-27 | Закрытое акционерное общество "ФЕРРОСПЛАВ" | Flux cored wire filler for out-of-furnace treatment of metallurgical melts |
| DE102012013662A1 (en) * | 2012-07-10 | 2014-01-16 | Mechthilde Döring-Freißmuth | Filled wire and process for the treatment of molten iron |
| CN106350703B (en) * | 2015-07-16 | 2018-07-10 | 东北大学 | A kind of method for preparing kalzium metal with electrolysis raw aluminum liquid fused salt thermal reduction |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE974835C (en) * | 1951-02-27 | 1961-05-10 | Max Planck Inst Eisenforschung | Process for deoxidizing iron and steel melts |
| DE1220617B (en) * | 1958-02-03 | 1966-07-07 | Res Inst Iron Steel | Master alloy for the production of fine-grained steels |
| DE2421743B2 (en) * | 1974-05-06 | 1979-06-07 | Ototani, Tohei, Sendai (Japan) | Process for producing a rod-shaped deoxidizing and desulfurizing agent for iron or steel melts or the like |
| AU4828279A (en) * | 1978-07-12 | 1980-01-17 | Lava Crucible-Refractories Co. | Introducing agents into a vessel of molten metal |
| DE2948636A1 (en) * | 1979-12-04 | 1981-06-11 | Metallgesellschaft Ag, 6000 Frankfurt | WIRE-SHAPED AGENT FOR TREATING METAL MELT |
| DE3169368D1 (en) * | 1980-07-09 | 1985-04-25 | Foseco Int | Metallurgical treatment agents |
| EP0137618B1 (en) * | 1983-08-12 | 1988-06-22 | Pfizer Inc. | Process and apparatus for adding calcium to a bath of molten ferrous material |
-
1986
- 1986-01-22 DE DE8686420021T patent/DE3661841D1/en not_active Expired
- 1986-01-22 WO PCT/FR1986/000017 patent/WO1986004359A1/en unknown
- 1986-01-22 AU AU53538/86A patent/AU587228B2/en not_active Ceased
- 1986-01-22 AT AT86420021T patent/ATE40154T1/en not_active IP Right Cessation
- 1986-01-22 EP EP86420021A patent/EP0190089B1/en not_active Expired
- 1986-07-28 ES ES556978A patent/ES8801386A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3661841D1 (en) | 1989-02-23 |
| WO1986004359A1 (en) | 1986-07-31 |
| AU5353886A (en) | 1986-08-13 |
| AU587228B2 (en) | 1989-08-10 |
| EP0190089A1 (en) | 1986-08-06 |
| ES556978A0 (en) | 1988-01-01 |
| ES8801386A1 (en) | 1988-01-01 |
| ATE40154T1 (en) | 1989-02-15 |
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