EP2152918B1 - Novel additive comprising lead and/or a lead alloy intended to treat baths of liquid steel - Google Patents
Novel additive comprising lead and/or a lead alloy intended to treat baths of liquid steel Download PDFInfo
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- EP2152918B1 EP2152918B1 EP08805930A EP08805930A EP2152918B1 EP 2152918 B1 EP2152918 B1 EP 2152918B1 EP 08805930 A EP08805930 A EP 08805930A EP 08805930 A EP08805930 A EP 08805930A EP 2152918 B1 EP2152918 B1 EP 2152918B1
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- lead
- liquid steel
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
Definitions
- the present invention relates to an additive in the form of cored wire for the treatment of liquid steel baths to obtain steels with a high content of lead.
- Lead is well known for improving the machinability of steels because, insoluble in steel, it forms exogenous inclusions of lead (nodules) which act as a lubricant and promote the division of chips during the machining of rolled steels.
- lead nodules
- it has significant disadvantages of use, given its toxicity, its high density (higher than that of liquid steel) and its low melting point. It is introduced into liquid steel baths by injection of balls or shots through a submerged lance or in the form of cored wire, the latter technique being known to be generally more flexible and more reliable.
- the document EP 0 316 921 describes a lead-containing additive for steel baths, in the form of a cored wire composed of a metallic sheath and a finely divided filling material, the latter containing metallic lead and / or lead alloys and a material containing lime and releasing carbon dioxide (CO 2 ) at the temperature of the liquid steel bath.
- the release of CO 2 in the steel bath produces, around the cored wire, an intense turbulence which has the effect of emulsifying the lead particles in the molten steel and driving them in motion inside the bath, thus improving their distribution in the liquid steel bath.
- the use of this additive has made it possible to limit the emissions of harmful fumes and to better control the addition process, while increasing the addition efficiency compared with those previously known.
- this type of additive does not allow to have, in the liquid steel ladle, a uniform distribution of lead inclusions throughout the casting. Furthermore, the final steel product obtained through the use of this additive does not have a homogeneous distribution of lead inclusions. In addition, the yield of the addition of lead in the molten steel bath always remains below 70%.
- the present invention aims to overcome these disadvantages by proposing a new additive comprising a lead and / or lead alloy powder whose size and particle size distribution are very specific, said powder being associated with a compound capable of ensure a homogeneous distribution of lead in the liquid steel bath.
- the subject of the invention is the use of the additive comprising metallic lead and / or one or more lead alloys, described above, for treating liquid steel baths.
- the invention also relates, according to a fourth aspect, to a rolled product made of steel with a high lead content obtained by the aforementioned process, characterized in that the lead nodules are less than 100 ⁇ m in size and, for the most part, up to at least 80%, distributed in the rolled steel according to a type of random distribution as shown in figure 3a . This distribution gives the rolled steel optimum machinability characteristics.
- this new additive makes it possible to very significantly improve the lead addition efficiencies and therefore the possibility of making greater additions under satisfactory hygiene and safety conditions. It also makes it possible to obtain a better distribution of the nodules of lead in final in the solid steel while decreasing the phenomena of remanence and contamination of the refractories of the pockets used for the treatment of these steels. The production costs of these steels are thus improved.
- the present invention relates to a novel additive comprising metallic lead and / or lead alloy (s) intended for the treatment of liquid steel baths with a view to obtaining steels with a high lead content.
- this additive is in the form of cored wire composed of a metal sheath and a finely divided filling material, the latter consisting of a metallic lead powder and / or lead alloy and a powder of a compound capable of releasing a gas, inert with respect to the liquid steel, at the temperature of the liquid steel bath.
- said metallic lead powder and / or lead alloy powder consists of a particle size fraction G R of between 200 ⁇ m and 500 ⁇ m.
- This granulometric fraction is preferably in the form of small granules or very fine beads.
- This granulometric distribution (contained in the area materialized at the figure 1 ) gives the cored wire optimum filling properties leading to an efficient metallurgical treatment of liquid steel baths.
- the choice of such a particle size distribution ensures a level of residual porosity much lower than those observed in cored wires made from a conventional lead powder.
- the porosity is thus between 5% and 20% maximum while for a conventional yarn, the value is generally between 15 and 40%.
- the metallic sheath surrounding the additive is formed of a material capable of dissolving in the steel bath with a speed sufficiently high to allow the release of said additive and without introducing unwanted components therein.
- the metal sheath is unalloyed mild steel. Its thickness is between 0.1 and 1 mm, preferably between 0.2 and 0.6 mm.
- the diameter of the cored wire according to the invention is between 5 and 20 mm, preferably between 9 and 15 mm.
- the additive according to the invention is in the form of cored wire containing from 100 to 1000 g of lead per meter of wire.
- the powder of compound able to spontaneously release a gas inert with respect to the liquid steel, at the temperature of the liquid steel bath (between about 1550 and 1650 ° C.), this is also present in finely divided form, with a particle size of less than 1 mm, preferably less than 0.5 mm.
- the release of the gas bubbles in the liquid steel bath creates an updraft which leads to a very random distribution of the lead inclusions formed from the particle size fraction according to the invention, thereby standardizing their distribution in the dye bath. liquid steel.
- the compound capable of spontaneously liberating a gas, inert with respect to the liquid steel is a mineral compound such as limestone (calcium carbonate) or uncured dolomite, and said inert gas by compared to liquid steel is carbon dioxide.
- the inorganic compound is used in an amount of 3 to 30% by weight relative to the weight of the lead metal and / or lead alloy or alloys used (s).
- the invention relates to a process for treating liquid steel baths with an additive comprising metallic lead and / or lead alloy (s), comprising a step of adding to said baths an additive in the form of the cored wire described above.
- a cored wire containing such a powder makes it possible to obtain a lead yield in the liquid steel greater than that obtained with a conventional wire or with that described in the document EP 0 316 921 .
- the figure 2 presents industrial results concerning the lead yield as a function of the quantities added (the variation of the lead yield as a function of the quantity of additive added to the steel bath expressed as the length of cored wire per tonne of steel).
- the cored wire containing the lead powder and / or a lead alloy whose particle size respects the specificities described in this invention makes it possible to obtain a higher lead yield than with a conventional powder. It also makes it possible to obtain very regular and constant yields regardless of the length of yarn injected into the liquid steel bath. Thus, the smaller dispersion makes it possible to very substantially increase the chances of success in obtaining the lead shot in the final steel.
- the addition of the additive according to the invention in the liquid steel ladle takes place before the casting.
- an amount of from 0.1 to 10 kg of additive in the form of cored wire per ton of liquid steel to be treated is introduced.
- the cored wire is discharged into the steel bath at a speed of 50 to 200 m / min, preferably 100 to 150 m / min.
- the particle size of the lead particles contained in the flux-cored wire has been chosen within a very small range of 200 to 500 ⁇ m, the lead inclusions, insoluble in the liquid steel, are distributed evenly throughout the pocket.
- the reduced size of the lead inclusions makes it possible to greatly reduce their sedimentation in the bottom of the pocket.
- the solidified product is therefore more homogeneous in lead content irrespective of the quantity of liquid steel remaining to flow. This is illustrated in the following example.
- loom refers to a solidified steel unit (round, rectangular, or polygonal steel ingot).
- the use of the cored wire containing a finely divided lead powder according to the invention makes it possible to reduce the washing operations of the bags used for the preparation of liquid steels with a high lead content.
- Pocket refractories are less polluted by heavy lead infiltration.
- the steelmaker notes fewer lead residues in the opening / closing systems of the taphole as well as in the joints between the refractory bricks.
- the scrap rate of rolled products (bars) of high lead steels is greatly reduced by the use of the additive containing a lead powder and / or lead alloy whose particle size is described herein. invention.
- the bars are discarded if the size and distribution of the lead nodules do not meet the specifications imposed by the client of the steelmaker.
- 100% of the bars are compliant while the use of a cored wire containing a conventional lead powder can cause up to 30% of scrap.
- the lead nodules are more suitably distributed in the rolled product thus promoting the machinability properties.
- the Applicant has specifically developed a criterion for qualifying the distribution of the population of lead nodules in rolled products. It has therefore defined distribution indices and the associated criteria and finally the conditions for experimental measurements.
- the lead nodules are distributed randomly (thus favoring machinability) when I R is greater than 1.4%.
- This index I R is relevant only if a large number of lead nodules are taken into account. This number has been fixed at 500. A specific method of analysis has thus been developed.
- the characterization of the lead nodules is carried out on the surface of a sample taken at mid-radius from a rolled steel bar with a larger diameter at 40 mm, and observed in the rolling direction.
- the surface of the sample taken is polished to 1 ⁇ m sheet.
- Lead nodules are identified and characterized by observation of the sample surface with a scanning electron microscope equipped with a backscattered electron detector (SEM-FEG) coupled to an image analyzer. With this mode of observation and thanks to the chemical contrast, lead nodules appear with a significantly higher average gray level than the steel matrix and inclusions of other types (such as sulphides, oxides, nitrides). .) which makes it possible to distinguish them and isolate them easily.
- SEM-FEG backscattered electron detector
- the measurement method consists in observing an area of at least 25 mm 2 , in a square-shaped area centered at mid-radius of the bar. All lead nodules with a small ferret diameter greater than 2 microns are taken into account and measured. More than 500 lead nodules must be taken into account. For each of these nodules, the position parameters (X and Y coordinates in the reference of the zone examined) and the main morphological parameters (surface of the nodule, diameter of Feret ...) are saved in a file of results.
- the distribution parameters are then calculated to highlight the distribution of lead nodules to optimize the machinability properties of the product.
- Several types of distributions represented in the figure 3 annexed, are taken into account: random ( Fig. 3a ), in clusters ( Fig. 3b ), in strips ( Fig. 3c ) or in a network ( Fig. 3d ).
- random Fig. 3a
- Fig. 3b in clusters
- Fig. 3c in strips
- Fig. 3d a network
- the proportion of nodules distributed according to the random type should be maximum. and preferably at least 80%.
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Abstract
Description
La présente invention concerne un additif sous forme de fil fourré destiné au traitement des bains d'acier liquide en vue d'obtenir des aciers à haute teneur en plomb.The present invention relates to an additive in the form of cored wire for the treatment of liquid steel baths to obtain steels with a high content of lead.
Le plomb est bien connu pour améliorer l'usinabilité des aciers car, non soluble dans l'acier, il forme des inclusions exogènes de plomb (nodules) qui agissent comme lubrifiant et favorisent la division des copeaux lors de l'usinage des aciers laminés. Il présente par contre d'importants inconvénients d'utilisation, compte tenu de sa toxicité, de sa forte densité (supérieure à celle de l'acier liquide) et de son bas point de fusion. Il est introduit dans les bains d'acier liquide par injection de billes ou de grenailles au travers d'une lance immergée ou bien sous forme de fil fourré, cette dernière technique étant connue pour être généralement plus souple et plus fiable.Lead is well known for improving the machinability of steels because, insoluble in steel, it forms exogenous inclusions of lead (nodules) which act as a lubricant and promote the division of chips during the machining of rolled steels. However, it has significant disadvantages of use, given its toxicity, its high density (higher than that of liquid steel) and its low melting point. It is introduced into liquid steel baths by injection of balls or shots through a submerged lance or in the form of cored wire, the latter technique being known to be generally more flexible and more reliable.
Les rendements d'addition obtenus aujourd'hui avec les fils fourrés classiques ne permettent pas de réaliser des ajouts importants de plomb, sous peine de générer d'importantes quantités de fumées nocives et en conséquence des gênes considérables vis-à-vis de l'hygiène et la sécurité des personnels.The addition efficiencies obtained today with the conventional flux cored wires do not make it possible to make significant additions of lead, under penalty of generating large quantities of harmful fumes and as a result considerable inconveniences vis-à-vis the hygiene and personal safety.
Le document
Cependant, il a été constaté que l'utilisation de ce type d'additif ne permet pas d'avoir, dans la poche d'acier liquide, une répartition uniforme des inclusions de plomb tout au long de la coulée. Par ailleurs, le produit final en acier obtenu grâce à l'utilisation de cet additif ne présente pas une distribution homogène des inclusions de plomb. En outre, le rendement de l'addition de plomb dans le bain d'acier liquide reste toujours en dessous de 70%.However, it has been found that the use of this type of additive does not allow to have, in the liquid steel ladle, a uniform distribution of lead inclusions throughout the casting. Furthermore, the final steel product obtained through the use of this additive does not have a homogeneous distribution of lead inclusions. In addition, the yield of the addition of lead in the molten steel bath always remains below 70%.
La présente invention a pour objectif de pallier à ces inconvénients en proposant un nouvel additif comprenant une poudre de plomb métallique et/ou d'alliage de plomb dont la taille et la répartition granulométrique sont très spécifiques, ladite poudre étant associée à un composé capable d'assurer une distribution homogène du plomb dans le bain d'acier liquide.The present invention aims to overcome these disadvantages by proposing a new additive comprising a lead and / or lead alloy powder whose size and particle size distribution are very specific, said powder being associated with a compound capable of ensure a homogeneous distribution of lead in the liquid steel bath.
A cet effet, l'invention concerne, selon un premier aspect, un additif comprenant du plomb métallique et/ou un ou des alliages de plomb, destiné à traiter des bains d'acier liquide, ledit additif se présentant sous forme de fil fourré composé d'une gaine métallique et d'une matière de remplissage finement divisée, cette dernière étant constituée d'une poudre de plomb métallique et/ou d'alliage de plomb et d'une poudre d'un composé apte à libérer un gaz, inerte par rapport à l'acier liquide, à la température du bain d'acier liquide, ledit additif étant caractérisé en ce que ladite poudre de plomb métallique et/ou d'alliage de plomb consiste en une fraction granulométrique GR comprise entre 200 µm et 500 µm et en ce que ladite fraction granulométrique GR présente les caractéristiques suivantes :
- au tamis de 200µm : GR ≤ 5% ;
- au tamis de 300µm : 90% ≥ GR ≥ 10% ;
- au tamis de 400µm : 40% ≤ GR ≤ 100% ;
- au tamis de 500µm : 100% ≥ GR ≥ 90%.
- with a sieve of 200 μm: G R ≤ 5%;
- 300μm sieve: 90% ≥ G R ≥ 10%;
- with a 400 μm screen: 40% ≤ G R ≤ 100%;
- 500μm sieve: 100% ≥ G R ≥ 90%.
Selon un deuxième aspect, l'invention a trait à un procédé de traitement des bains d'acier liquide au moyen d'un additif comprenant du plomb métallique et/ou un ou des alliages de plomb, comprenant une étape d'addition aux dits bains d'acier d'un additif se présentant sous forme de fil fourré composé d'une gaine métallique et d'une matière de remplissage finement divisée, cette dernière étant constituée d'une poudre de plomb métallique et/ou d'alliage de plomb et d'une poudre d'un composé apte à libérer un gaz, inerte par rapport à l'acier liquide, à la température du bain d'acier liquide, ladite poudre de plomb métallique et/ou d'alliage de plomb consistant en une fraction granulométrique GR qui est comprise entre 200 µm et 500 µm et qui présente les caractéristiques suivantes :
- au tamis de 200µm : GR ≤ 5% ;
- au tamis de 300µm : 90% ≥ GR ≥ 10% ;
- au tamis de 400µm : 40% ≤ GR ≤ 100% ;
- au tamis de 500µm : 100% ≥ GR ≥ 90%.
- with a sieve of 200 μm: G R ≤ 5%;
- 300μm sieve: 90% ≥ G R ≥ 10%;
- with a 400 μm screen: 40% ≤ G R ≤ 100%;
- 500μm sieve: 100% ≥ G R ≥ 90%.
Selon un troisième aspect, l'invention a pour objet l'utilisation de l'additif comprenant du plomb métallique et/ou un ou des alliages de plomb, décrit plus haut, pour traiter des bains d'acier liquide.According to a third aspect, the subject of the invention is the use of the additive comprising metallic lead and / or one or more lead alloys, described above, for treating liquid steel baths.
L'invention concerne également, selon un quatrième aspect, tout produit laminé en acier à haute teneur en plomb obtenu par le procédé précité, caractérisé en ce que les nodules de plomb sont de taille inférieure à 100 µm et très majoritairement, à hauteur d'au moins 80%, distribués dans l'acier laminé selon un type de répartition aléatoire tel que représenté à la
L'utilisation de ce nouvel additif permet d'améliorer très sensiblement les rendements d'addition de plomb et par la même la possibilité de faire des ajouts plus importants dans des conditions d'hygiène et de sécurité satisfaisantes. Elle permet également d'obtenir une meilleure répartition des nodules de plomb en final dans l'acier solide tout en diminuant les phénomènes de rémanence et contamination des réfractaires des poches utilisées pour le traitement de ces aciers. Les coûts de production de ces aciers sont ainsi améliorés.The use of this new additive makes it possible to very significantly improve the lead addition efficiencies and therefore the possibility of making greater additions under satisfactory hygiene and safety conditions. It also makes it possible to obtain a better distribution of the nodules of lead in final in the solid steel while decreasing the phenomena of remanence and contamination of the refractories of the pockets used for the treatment of these steels. The production costs of these steels are thus improved.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description détaillée et des exemples de réalisation qui vont suivre, ainsi que des figures annexées dans lesquelles :
- la
figure 1 représente les caractéristiques de tailles et de répartitions granulométriques de la fraction granulométrique GR ; - la
figure 2 présente la variation du rendement en plomb en fonction de la quantité d'additif ajouté au bain d'acier exprimée en longueur de fil fourré ajoutée par tonne d'acier liquide ; - la
figure 3 représente de manière schématique les différents types de répartitions des nodules de plomb dans le produit final en acier solide ; - la
figure 4 représente un diagramme permettant le calcul de la distance minimale avec le nodule de plomb le plus proche.
- the
figure 1 represents the characteristics of sizes and particle size distributions of the grain size fraction G R ; - the
figure 2 shows the variation in lead yield as a function of the amount of additive added to the steel bath expressed as the length of flux-cored wire added per tonne of liquid steel; - the
figure 3 schematically represents the different types of distribution of lead nodules in the final solid steel product; - the
figure 4 represents a diagram allowing the calculation of the minimum distance with the nearest lead nodule.
La présente invention concerne un nouvel additif comprenant du plomb métallique et/ou un ou des alliages de plomb, destiné au traitement de bains d'acier liquide en vue d'obtenir des aciers à haute teneur en plomb. De manière connue, cet additif se présente sous forme de fil fourré composé d'une gaine métallique et d'une matière de remplissage finement divisée, cette dernière étant constituée d'une poudre de plomb métallique et/ou d'alliage de plomb et d'une poudre d'un composé apte à libérer un gaz, inerte par rapport à l'acier liquide, à la température du bain d'acier liquide.The present invention relates to a novel additive comprising metallic lead and / or lead alloy (s) intended for the treatment of liquid steel baths with a view to obtaining steels with a high lead content. In known manner, this additive is in the form of cored wire composed of a metal sheath and a finely divided filling material, the latter consisting of a metallic lead powder and / or lead alloy and a powder of a compound capable of releasing a gas, inert with respect to the liquid steel, at the temperature of the liquid steel bath.
Avantageusement, ladite poudre de plomb métallique et/ou d'alliage de plomb consiste en une fraction granulométrique GR comprise entre 200 µm et 500 µm. Cette fraction granulométrique se présente de préférence sous forme de petits granulés ou de billes très fines.Advantageously, said metallic lead powder and / or lead alloy powder consists of a particle size fraction G R of between 200 μm and 500 μm. This granulometric fraction is preferably in the form of small granules or very fine beads.
De manière caractérisante, ladite fraction granulométrique GR présente les caractéristiques suivantes :
- au tamis de 200µm : GR ≤ 5% ;
- au tamis de 300µm : 90% ≥ GR ≥ 10% ;
- au tamis de 400µm : 40% ≤ GR ≤ 100% ;
- au tamis de 500µm : 100% ≥ GR ≥ 90%.
- with a sieve of 200 μm: G R ≤ 5%;
- 300μm sieve: 90% ≥ G R ≥ 10%;
- with a 400 μm screen: 40% ≤ G R ≤ 100%;
- 500μm sieve: 100% ≥ G R ≥ 90%.
Ces caractéristiques granulométriques sont représentées schématiquement dans la
Cette répartition granulométrique (contenue dans l'aire matérialisée à la
La gaine métallique entourant l'additif est formée en un matériau apte à se dissoudre dans le bain d'acier avec une vitesse suffisamment élevée pour permettre la libération dudit additif et sans y introduire des composants non désirés. De préférence, la gaine métallique est en acier doux non allié. Son épaisseur est comprise entre 0,1 et 1 mm, de préférence entre 0,2 et 0,6 mm.The metallic sheath surrounding the additive is formed of a material capable of dissolving in the steel bath with a speed sufficiently high to allow the release of said additive and without introducing unwanted components therein. Preferably, the metal sheath is unalloyed mild steel. Its thickness is between 0.1 and 1 mm, preferably between 0.2 and 0.6 mm.
Par ailleurs, le diamètre du fil fourré selon l'invention est compris entre 5 et 20 mm, de préférence entre 9 et 15 mm.Furthermore, the diameter of the cored wire according to the invention is between 5 and 20 mm, preferably between 9 and 15 mm.
L'additif selon l'invention se présente sous forme de fil fourré contenant de 100 à 1000 g de plomb par mètre de fil.The additive according to the invention is in the form of cored wire containing from 100 to 1000 g of lead per meter of wire.
S'agissant de la poudre de composé apte à libérer spontanément un gaz, inerte par rapport à l'acier liquide, à la température du bain d'acier liquide (comprise entre 1550 et 1650 °C environ), celle-ci est également présente sous forme finement divisée, avec une taille des particules inférieure à 1 mm, de préférence inférieure à 0,5 mm.With regard to the powder of compound able to spontaneously release a gas, inert with respect to the liquid steel, at the temperature of the liquid steel bath (between about 1550 and 1650 ° C.), this is also present in finely divided form, with a particle size of less than 1 mm, preferably less than 0.5 mm.
Avantageusement, la libération des bulles de gaz dans le bain d'acier liquide crée un courant ascendant qui conduit à une répartition très aléatoire des inclusions de plomb formées à partir de la fraction granulométrique selon l'invention, uniformisant ainsi leur distribution dans le bain d'acier liquide.Advantageously, the release of the gas bubbles in the liquid steel bath creates an updraft which leads to a very random distribution of the lead inclusions formed from the particle size fraction according to the invention, thereby standardizing their distribution in the dye bath. liquid steel.
Dans un mode particulier de réalisation, le composé apte à libérer spontanément un gaz, inerte par rapport à l'acier liquide, est un composé minéral tel que du calcaire (carbonate de calcium) ou de la dolomie non cuite, et ledit gaz inerte par rapport à l'acier liquide est le dioxyde de carbone. Dans ce cas, le composé minéral est utilisé en une quantité de 3 à 30% en poids par rapport au poids du plomb métallique et/ou de l'alliage ou des alliages de plomb utilisé(s).In a particular embodiment, the compound capable of spontaneously liberating a gas, inert with respect to the liquid steel, is a mineral compound such as limestone (calcium carbonate) or uncured dolomite, and said inert gas by compared to liquid steel is carbon dioxide. In this case, the inorganic compound is used in an amount of 3 to 30% by weight relative to the weight of the lead metal and / or lead alloy or alloys used (s).
Selon un deuxième aspect, l'invention a trait à un procédé de traitement des bains d'acier liquide au moyen d'un additif comprenant du plomb métallique et/ou un ou des alliages de plomb, comprenant une étape d'addition aux dits bains d'un additif se présentant sous forme du fil fourré décrit plus haut.According to a second aspect, the invention relates to a process for treating liquid steel baths with an additive comprising metallic lead and / or lead alloy (s), comprising a step of adding to said baths an additive in the form of the cored wire described above.
Un fil fourré contenant une telle poudre permet d'obtenir un rendement en plomb dans l'acier liquide supérieur à celui obtenu avec un fil classique ou encore avec celui décrit dans le document
La
Le rendement en plomb est défini par l'équation suivante :
Dans cette équation:
- CI est la teneur initiale en plomb dans la poche d'acier liquide ;
- CF est la teneur finale en plomb obtenue dans la poche d'acier liquide ;
- CA est la teneur visée en plomb dans la poche d'acier liquide ;
- YPb est le rendement de l'addition de plomb.
In this equation:
- C I is the initial lead content in the liquid steel ladle;
- C F is the final lead content obtained in the liquid steel ladle;
- C A is the target lead content in the liquid steel ladle;
- Y Pb is the yield of the addition of lead.
Le fil fourré contenant la poudre de plomb et/ou un alliage de plomb dont la granulométrie respecte les spécificités décrites dans cette invention permet d'obtenir un rendement de plomb plus élevé qu'avec une poudre classique. Il permet également d'obtenir des rendements très réguliers et constants quelle que soit la longueur de fil injectée dans le bain d'acier liquide. Ainsi la dispersion plus réduite permet d'accroître très sensiblement les chances de réussite d'obtention de la visée en plomb dans l'acier final.The cored wire containing the lead powder and / or a lead alloy whose particle size respects the specificities described in this invention makes it possible to obtain a higher lead yield than with a conventional powder. It also makes it possible to obtain very regular and constant yields regardless of the length of yarn injected into the liquid steel bath. Thus, the smaller dispersion makes it possible to very substantially increase the chances of success in obtaining the lead shot in the final steel.
Grâce à un rendement plus élevé, les conditions d'hygiène et de sécurité lors du traitement des poches d'acier liquide se trouvent en outre sensiblement améliorées. Il y a moins de dégagement de fumées nocives au-dessus de la poche. Les phénomènes de sédimentation du plomb en fond de poche et de pollution des parois réfractaires de poches sont également fortement réduits.Thanks to a higher efficiency, the hygiene and safety conditions during the treatment of the liquid steel bags are also substantially improved. There is less release of harmful fumes over the pocket. The phenomena of sedimentation of lead in the bottom of the pocket and pollution of the refractory pockets walls are also greatly reduced.
L'ajout de l'additif selon l'invention dans la poche d'acier liquide a lieu avant la coulée. Selon la teneur finale en plomb souhaitée, on introduit une quantité allant de 0,1 à 10 kg d'additif sous forme de fil fourré par tonne d'acier liquide à traiter. Le fil fourré est dévidé dans le bain d'acier à une vitesse allant de 50 à 200 m/min, de préférence de 100 à 150 m/min.The addition of the additive according to the invention in the liquid steel ladle takes place before the casting. Depending on the desired final lead content, an amount of from 0.1 to 10 kg of additive in the form of cored wire per ton of liquid steel to be treated is introduced. The cored wire is discharged into the steel bath at a speed of 50 to 200 m / min, preferably 100 to 150 m / min.
Les deux exemples suivants illustrent les valeurs élevées du rendement en plomb obtenues grâce à l'utilisation du nouvel additif selon l'invention.The following two examples illustrate the high values of lead yield obtained through the use of the new additive according to the invention.
- Fil fourré de 13,6 mm de diamètre extérieur13.6 mm outer diameter cored wire
- Epaisseur de feuillard comprise entre 0,35 et 0,40 mmThickness of strip between 0.35 and 0.40 mm
- Quantité de carbonate de calcium dans le mélange : 6,3% en poidsAmount of calcium carbonate in the mixture: 6.3% by weight
- Poids métrique du fil : 970 g/mMetric weight of the thread: 970 g / m
- Vitesse d'injection : 120 m/minInjection speed: 120 m / min
- Poids d'acier liquide en poche : 95 tLiquid steel weight in pocket: 95 t
- Teneur en plomb visée : 0,260%Targeted lead content: 0,260%
- Teneur en plomb obtenue après traitement : 0, 248%Lead content obtained after treatment: 0, 248%
- Le rendement de l'addition de plomb en fil fourré obtenu est de : 71,8%The yield of the addition of lead to cored wire obtained is: 71.8%
- Fil fourré de 13,6 mm de diamètre extérieur13.6 mm outer diameter cored wire
- Epaisseur de feuillard comprise entre 0,35 et 0,40 mmThickness of strip between 0.35 and 0.40 mm
- Quantité de carbonate de calcium dans le mélange : 5,8% en poidsAmount of calcium carbonate in the mixture: 5.8% by weight
- Longueur de fil injectée : 334 mThread length injected: 334 m
- Vitesse d'injection fil : 150 m/minThread injection speed: 150 m / min
- Poids d'acier liquide en poche : 115 tLiquid steel weight in pocket: 115 t
- Teneur en plomb visée : 0,200%Targeted lead content: 0.200%
- Teneur en plomb initiale dans le bain d'acier liquide : 0,009%Initial lead content in the liquid steel bath: 0.009%
- Teneur en plomb obtenue après traitement : 0,191%Lead content obtained after treatment: 0.191%
- Le rendement de l'addition de plomb en fil fourré obtenu est de : 72,0%.The yield of the addition of lead in cored wire obtained is: 72.0%.
Parce que la granulométrie des particules de plomb contenues dans le fil fourré a été choisie dans un intervalle très restreint de 200 à 500 µm, les inclusions de plomb, insolubles dans l'acier liquide, se répartissent de manière uniforme dans toute la poche.Because the particle size of the lead particles contained in the flux-cored wire has been chosen within a very small range of 200 to 500 μm, the lead inclusions, insoluble in the liquid steel, are distributed evenly throughout the pocket.
Avantageusement, la taille réduite des inclusions de plomb permet de diminuer fortement leur sédimentation en fond de poche. Ceci conduit à avoir une teneur en plomb constante dans le bain d'acier liquide depuis le début de la vidange de la poche jusqu'à la fin de la coulée. Le produit solidifié est donc plus homogène en teneur en plomb quelle que soit la quantité d'acier liquide restant à couler. Ceci est illustré dans l'exemple suivant.Advantageously, the reduced size of the lead inclusions makes it possible to greatly reduce their sedimentation in the bottom of the pocket. This leads to a constant lead content in the liquid steel bath from the beginning of the emptying of the pocket until the end of the casting. The solidified product is therefore more homogeneous in lead content irrespective of the quantity of liquid steel remaining to flow. This is illustrated in the following example.
- Fil fourré de 13,6 mm de diamètre extérieur13.6 mm outer diameter cored wire
- Epaisseur de feuillard comprise entre 0,35 et 0,40 mmThickness of strip between 0.35 and 0.40 mm
- Quantité de carbonate de calcium dans le mélange : 6,5% en poidsAmount of calcium carbonate in the mixture: 6.5% by weight
- Quantité de poudre injectée par fil fourré : 297 kgQuantity of powder injected by cored wire: 297 kg
- Vitesse d'injection fil : 120 m/minThread injection speed: 120 m / min
- Poids poche : 95 tPocket weight: 95 t
- Teneur en plomb visée : 0,260%Targeted lead content: 0,260%
- Teneur en plomb obtenue sur les premiers blooms coulés : 0,252%Lead content obtained on the first cast blooms: 0.252%
- Teneur en plomb obtenue sur blooms en milieu de poche : 0,245%Lead content obtained on blooms in the middle of the pocket: 0.245%
- Teneur en plomb obtenue sur blooms en fin de vidange poche : 0,249%.Lead content obtained on blooms at the end of emptying pocket: 0.249%.
Le terme « bloom » désigne une unité d'acier solidifié (lingot d'acier de section ronde, rectangulaire, ou polygonale).The term "bloom" refers to a solidified steel unit (round, rectangular, or polygonal steel ingot).
Par ailleurs, l'utilisation du fil fourré contenant une poudre de plomb finement divisée selon l'invention permet de diminuer les opérations de lavage des poches utilisées pour l'élaboration des aciers liquides à haute teneur en plomb. Les réfractaires de poche sont moins pollués par des infiltrations importantes de plomb. L'aciériste constate moins de résidus de plomb dans les systèmes d'ouverture/fermeture du trou de coulée ainsi que dans les joints entre les briques réfractaires.Furthermore, the use of the cored wire containing a finely divided lead powder according to the invention makes it possible to reduce the washing operations of the bags used for the preparation of liquid steels with a high lead content. Pocket refractories are less polluted by heavy lead infiltration. The steelmaker notes fewer lead residues in the opening / closing systems of the taphole as well as in the joints between the refractory bricks.
Le taux de rebuts des produits laminés (barres) en aciers à haute teneur en plomb est fortement abaissé grâce à l'utilisation de l'additif contenant une poudre de plomb et/ou d'alliage de plomb dont la granulométrie est décrite dans la présente invention. Les barres sont rebutées si la taille et la répartition des nodules de plomb ne répondent pas au cahier des charges imposé par le client du sidérurgiste. Grâce à l'additif selon l'invention, 100% des barres sont conformes alors que l'utilisation d'un fil fourré contenant une poudre de plomb classique peut entraîner jusqu'à 30% de rebus.The scrap rate of rolled products (bars) of high lead steels is greatly reduced by the use of the additive containing a lead powder and / or lead alloy whose particle size is described herein. invention. The bars are discarded if the size and distribution of the lead nodules do not meet the specifications imposed by the client of the steelmaker. With the additive according to the invention, 100% of the bars are compliant while the use of a cored wire containing a conventional lead powder can cause up to 30% of scrap.
Outre des tailles plus petites, les nodules de plomb sont répartis de manière plus adéquate dans le produit laminé favorisant ainsi les propriétés d'usinabilité. Il n'existe pas de méthodes standard ou internationales pour caractériser la répartition des nodules de plomb dans les produits laminés; c'est pourquoi, nous avons développé spécifiquement un critère de qualification de la répartition de la population des nodules de plomb dans les produits laminés.In addition to smaller sizes, the lead nodules are more suitably distributed in the rolled product thus promoting the machinability properties. There are no standard or international methods for characterizing the distribution of lead nodules in laminates; that's why we have specifically developed a criterion for qualifying the distribution of the population of lead nodules in rolled products.
C'est pourquoi, la demanderesse a développé spécifiquement un critère de qualification de la répartition de la population des nodules de plomb dans les produits laminés. Elle a donc défini des indices de répartition et les critères associés et enfin les conditions de mesures expérimentales.Therefore, the Applicant has specifically developed a criterion for qualifying the distribution of the population of lead nodules in rolled products. It has therefore defined distribution indices and the associated criteria and finally the conditions for experimental measurements.
Grâce à une étude approfondie par simulation numérique modélisant les différentes répartitions envisagées
L'indice IR est défini comme suit :
Où :
- IR : indice de répartition
- D : diagonale de la zone d'analyse
- di : distance minimale entre les nodules de plomb (les plus proches voisins -
Fig. 4 ) - NI : nombre de nodules de plomb avec une distance minimale associée.
The index I R is defined as follows:
Or :
- I R : distribution index
- D : diagonal of the analysis area
- d i : minimum distance between lead nodules (nearest neighbors -
Fig. 4 ) - NI: number of lead nodules with a minimal distance associated.
Les nodules de plomb sont répartis de manière aléatoire (favorisant ainsi l'usinabilité) lorsque IR est supérieur à 1,4%.The lead nodules are distributed randomly (thus favoring machinability) when I R is greater than 1.4%.
Cet indice IR n'est pertinent qu'à condition de prendre en compte un nombre élevé de nodules de plomb. Ce nombre a été fixé à 500. Une méthode d'analyse spécifique a ainsi été developpée.This index I R is relevant only if a large number of lead nodules are taken into account. This number has been fixed at 500. A specific method of analysis has thus been developed.
La caractérisation des nodules de plomb est réalisée sur la surface d'un échantillon prélevé à mi-rayon d'une barre d'acier laminé d'un diamètre supérieur à 40 mm, et observé dans le sens de laminage. La surface de l'échantillon prélevé est polie jusqu'au drap de 1 µm.The characterization of the lead nodules is carried out on the surface of a sample taken at mid-radius from a rolled steel bar with a larger diameter at 40 mm, and observed in the rolling direction. The surface of the sample taken is polished to 1 μm sheet.
Les nodules de plomb sont identifiés et caractérisés par une observation de la surface de l'échantillon avec un microscope électronique à balayage équipé d'un détecteur d'électrons rétrodiffusés (MEB-FEG) couplé à un analyseur d'images. Avec ce mode d'observation et grâce au contraste chimique, les nodules de plomb apparaissent avec un niveau de gris moyen nettement supérieur à celui de la matrice d'acier et des inclusions d'autres natures (tels que sulfures, oxydes, nitrures...) ce qui permet de les distinguer et de les isoler aisément.Lead nodules are identified and characterized by observation of the sample surface with a scanning electron microscope equipped with a backscattered electron detector (SEM-FEG) coupled to an image analyzer. With this mode of observation and thanks to the chemical contrast, lead nodules appear with a significantly higher average gray level than the steel matrix and inclusions of other types (such as sulphides, oxides, nitrides). .) which makes it possible to distinguish them and isolate them easily.
La méthode de mesure consiste à observer une surface d'un minimum de 25 mm2, dans une zone de forme carrée centrée à mi-rayon de la barre. Tous les nodules de plomb avec un petit diamètre de Féret supérieur à 2 microns sont pris en compte et mesurés. Plus de 500 nodules de plomb doivent être pris en compte. Pour chacun de ces nodules, les paramètres de position (coordonnées X et Y dans le repère de la zone examinée) et les paramètres morphologiques principaux (surface du nodule, diamètre de Féret...) sont sauvegardés dans un fichier de résultats.The measurement method consists in observing an area of at least 25 mm 2 , in a square-shaped area centered at mid-radius of the bar. All lead nodules with a small ferret diameter greater than 2 microns are taken into account and measured. More than 500 lead nodules must be taken into account. For each of these nodules, the position parameters (X and Y coordinates in the reference of the zone examined) and the main morphological parameters (surface of the nodule, diameter of Feret ...) are saved in a file of results.
Les paramètres de répartition sont alors calculés afin de mettre en évidence la répartition des nodules de plomb permettant d'optimiser les propriétés d'usinabilité du produit. Plusieurs types de répartitions, représentées dans la
L'utilisation d'un additif se présentant sous forme de fil fourré contenant une poudre de plomb dont la granulométrie est telle que définie à la
L'utilisation du nouvel additif comprenant du plomb métallique et/ou un alliage de plomb, selon l'invention, pour traiter les poches d'acier liquide en vue d'obtenir des aciers à haute teneur en plomb présente de nombreux avantages et conduit notamment à :
- l'amélioration du rendement de l'addition de plomb dans le bain d'acier liquide;
- l'amélioration des conditions d'élaboration et de traitement des aciers à haute teneur en plomb : en effet l'accroissement du rendement d'addition permet de réduire l'émission des fumées nocives et donc une amélioration des conditions d'hygiène et de sécurité pour le personnel d'aciérie;
- une forte amélioration de la distribution et de la finesse des inclusions de plomb dans l'acier liquide qui permet de maintenir constante la teneur en plomb de l'acier du début de la coulée jusqu'à la vidange complète de la poche;
- une forte diminution de la sédimentation du plomb en fond de poche et ainsi une quasi disparition des résidus de plomb dans les systèmes d'ouverture/fermeture des trous de coulée ainsi que dans les joints des briques réfractaires;
- l'amélioration des propriétés finales d'usinabilité des produits en acier laminé grâce à une meilleure distribution des nodules de plomb dans l'acier laminé selon une répartition très majoritairement de type aléatoire, caractérisée par une méthode innovante développée spécialement pour palier à l'absence de méthode standard internationale;
- la forte réduction des taux de rebuts des produits laminés pour défauts internes liés à la présence de nodules de plomb de grande taille non désirables et/ou mal répartis dans les produits en acier laminés.
- improving the efficiency of the addition of lead in the liquid steel bath;
- the improvement of the conditions of elaboration and treatment of steels with a high lead content: indeed, the increase in the addition yield makes it possible to reduce the emission of harmful fumes and thus an improvement of the health and safety conditions for steelworks personnel;
- a strong improvement in the distribution and fineness of the lead inclusions in the liquid steel which makes it possible to keep the lead content of the steel constant from the beginning of the casting until the complete emptying of the pocket;
- a strong decrease in the sedimentation of lead in the bottom of the pocket and thus a virtual disappearance of the lead residues in the opening / closing systems of the tapholes as well as in the joints of the refractory bricks;
- the improvement of the final machinability properties of rolled steel products thanks to a better distribution of lead nodules in rolled steel in a predominantly random distribution, characterized by an innovative method specially developed to overcome the absence international standard method;
- the strong reduction in the rejection rates of rolled products for internal defects related to the presence of large lead nodules that are undesirable and / or poorly distributed in rolled steel products.
Claims (13)
- Additive comprising metallic lead and/or one or more lead alloys, for treating baths of liquid steel, said additive being in the form of flux-cored wire composed of a metal sheath and a finely-divided filling material, the latter being formed of a metallic lead powder and/or lead alloy powder and of a powder containing a material able to release a gas, which is inert with respect to the liquid steel, at the temperature of the bath of liquid steel, said additive being characterised in that said metallic lead powder and/or lead alloy powder consists of a particle size fraction GR between 200 µm and 500 µm, and in that said particle size fraction GR has the following characteristics:- through a 200 µm sieve: GR ≤ 5 %;- through a 300 µm sieve: 90 % ≥ GR ≥ 10 %;- through a 400 µm sieve: 40 % ≤ GR ≤ 100 %;- through a 500 µm sieve: 100 %≥ GR ≥ 90 %.
- Additive according to claim 1, wherein the metal sheath is made of unalloyed mild steel.
- Additive according to either claim 1 or claim 2, wherein the metal sheath is from 0.1 to 1 mm thick, preferably from 0.2 to 0.5 mm thick.
- Additive according to any one of claims 1 to 3, wherein the flux-cored wire has a diameter from 5 to 20 mm, preferably from 9 to 15 mm.
- Additive according to any one of claims 1 to 4, wherein the filling material has a particle size which does not exceed 1 mm.
- Additive according to any one of claims 1 to 5, wherein the flux-cored wire contains from 100 to 1000 g of lead per metre.
- Additive according to any one of claims 1 to 6, wherein the material able to release a gas, which is inert with respect to the liquid steel, is a mineral compound formed of limestone (calcium carbonate) or non-calcined dolomite, the gas released thus being carbon dioxide.
- Additive according to claim 7, wherein the mineral material is present in an amount of 3 to 30 % by weight based on the weight of lead or lead alloy (or alloys) used.
- Method for treating baths of liquid steel using an additive comprising metallic lead and/or one or more lead alloys, the method comprising a step of adding to said bath an additive in the form of a flux-cored wire composed of a metal sheath and a finely-divided filing material, the latter being formed of a metallic lead powder and/or lead alloy powder and of a powder of a material able to release a gas, which is inert with respect to the liquid steel, at the temperature of the bath of liquid steel, said metallic lead powder and/or lead alloy powder consisting of a particle size fraction GR between 200 µm and 500 µm and having the following characteristics:- through a 200 µm sieve: GR ≤ 5 %;- through a 300 µm sieve: 90 % ≥ GR ≥ 10 %;- through a 400 µm sieve: 40 % s GR ≤ 100 %;- thorough a 500 µm sieve: 100 % ≥ GR ≥ 90 %.
- Method according to claim 9, wherein 0.1 to 10 kg of flux-cored wire is added per tonne of liquid steel to be treated.
- Method according to either claim 10 or claim 11, wherein the flux-cored wire is added to the bath of liquid steel at a speed of 50 to 200 m/min, preferably of 100 to 150 m/min.
- Use of an additive comprising metallic lead and/or one or more lead alloys according to any one of claims 1 to 8, for treating baths of liquid steel.
- Rolled steel product having a high lead content and containing lead nodules smaller than 100 µm, obtained by the method according to any one of claims 9 to 11, characterised in that, when the distribution of the nodules is defined corresponding to the following formula:
where:IR : distribution indexD: diagonal of the analysis zoneDI : minimum distance between the closest lead nodulesNI: number of lead nodules with an associated minimum distance,IR is greater than 1.4%.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0755486A FR2917096B1 (en) | 2007-06-05 | 2007-06-05 | NOVEL ADDITIVE COMPRISING LEAD AND / OR LEAD ALLOY FOR TREATING LIQUID STEEL BATHS. |
PCT/FR2008/050989 WO2008152328A1 (en) | 2007-06-05 | 2008-06-04 | Novel additive comprising lead and/or a lead alloy for treating baths of liquid steel |
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EP2152918A1 EP2152918A1 (en) | 2010-02-17 |
EP2152918B1 true EP2152918B1 (en) | 2012-08-15 |
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EP08805930A Active EP2152918B1 (en) | 2007-06-05 | 2008-06-04 | Novel additive comprising lead and/or a lead alloy intended to treat baths of liquid steel |
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US (1) | US20100172787A1 (en) |
EP (1) | EP2152918B1 (en) |
JP (1) | JP5466153B2 (en) |
ES (1) | ES2392736T3 (en) |
FR (1) | FR2917096B1 (en) |
MX (1) | MX2009013264A (en) |
WO (1) | WO2008152328A1 (en) |
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CN102329916A (en) * | 2011-05-03 | 2012-01-25 | 首钢贵阳特殊钢有限责任公司 | Method for feeding lead compound core spun yarn |
CN106756635A (en) * | 2016-12-30 | 2017-05-31 | 山西太钢不锈钢股份有限公司 | A kind of preparation method containing tellurium steel and its steel containing tellurium |
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GB520072A (en) * | 1938-04-30 | 1940-04-12 | Inland Steel Co | A method of adding lead to steel |
US2151255A (en) * | 1939-01-03 | 1939-03-21 | Lufkin Rule Co | Spring nut |
US2259342A (en) * | 1940-04-17 | 1941-10-14 | Inland Steel Co | Method of adding lead to steel |
FR1537717A (en) * | 1967-05-05 | 1968-08-30 | Transformation Des Plastiques | Bodyguard |
US4056387A (en) * | 1974-08-14 | 1977-11-01 | Inland Steel Company | Leaded steel bar free of lead macroinclusions |
US4122771A (en) * | 1977-04-13 | 1978-10-31 | General Dynamics | Squeegee holder |
JPS5992151A (en) * | 1982-11-18 | 1984-05-28 | Sumitomo Metal Ind Ltd | Production of free-cutting lead steel by continuous casting method |
JPS59157215A (en) * | 1983-02-26 | 1984-09-06 | Nippon Steel Corp | Manufacture of molten steel containing lead by utilizing calcium carbonate |
JPS613822A (en) * | 1984-06-19 | 1986-01-09 | Nippon Kokan Kk <Nkk> | Method for adding alloy element of which vapor pressure is increased by temperature of molten steel to molten steel |
DE3739154A1 (en) * | 1987-11-19 | 1989-06-01 | Sueddeutsche Kalkstickstoff | LEADING ADDITIVE FOR STEEL MELTING |
JP2572807B2 (en) * | 1988-04-25 | 1997-01-16 | 新日本製鐵株式会社 | Manufacturing method of lead free-cutting steel by continuous casting method |
JPH03134111A (en) * | 1989-10-19 | 1991-06-07 | Nippon Steel Corp | Filling wire for treating molten metal treatable at a constant depth |
JPH04308021A (en) * | 1991-04-04 | 1992-10-30 | Kobe Steel Ltd | Production of lead-containing steel |
JPH06198490A (en) * | 1993-01-08 | 1994-07-19 | Nippon Steel Weld Prod & Eng Co Ltd | Production of additive cored wire |
US5458060A (en) * | 1993-05-03 | 1995-10-17 | Sony Electronics Inc. | Screen printing squeegee system |
US5695842A (en) * | 1996-04-23 | 1997-12-09 | Pawling Corporation | Entrance grating |
JP2000328132A (en) * | 1999-05-19 | 2000-11-28 | Namariichi Kagaku Kogyo Kk | Additive for adding lead into molten steel |
JP4228901B2 (en) * | 2003-12-08 | 2009-02-25 | 住友金属工業株式会社 | Method for continuous casting of molten metal |
JP4179180B2 (en) * | 2004-02-04 | 2008-11-12 | 住友金属工業株式会社 | Method and apparatus for continuous casting of molten metal |
FR2871477B1 (en) * | 2004-06-10 | 2006-09-29 | Affival Sa Sa | WIRE FOURRE |
JP4770616B2 (en) * | 2006-07-13 | 2011-09-14 | 住友金属工業株式会社 | Method for continuous casting of molten metal and immersion lance for continuous casting |
JP4844376B2 (en) * | 2006-12-11 | 2011-12-28 | 住友金属工業株式会社 | Method for continuous casting of molten metal |
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- 2008-06-04 US US12/663,070 patent/US20100172787A1/en not_active Abandoned
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FR2917096A1 (en) | 2008-12-12 |
US20100172787A1 (en) | 2010-07-08 |
ES2392736T3 (en) | 2012-12-13 |
JP2010529297A (en) | 2010-08-26 |
FR2917096B1 (en) | 2011-03-11 |
JP5466153B2 (en) | 2014-04-09 |
EP2152918A1 (en) | 2010-02-17 |
MX2009013264A (en) | 2010-02-18 |
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