EP0233872B1 - Method for the treatment of metals and alloys for the refining thereof - Google Patents

Method for the treatment of metals and alloys for the refining thereof Download PDF

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EP0233872B1
EP0233872B1 EP85905413A EP85905413A EP0233872B1 EP 0233872 B1 EP0233872 B1 EP 0233872B1 EP 85905413 A EP85905413 A EP 85905413A EP 85905413 A EP85905413 A EP 85905413A EP 0233872 B1 EP0233872 B1 EP 0233872B1
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alloy
refining
process according
nickel
added
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EP0233872A1 (en
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Gérard Bienvenu
Michel Jehan
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Extramet Industrie SA
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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel

Definitions

  • the present invention relates to a process for the treatment of metals and alloys, more particularly but not exclusively of ferrous metals and alloys, in particular those having a high melting point, for example greater than 1000 ° C.
  • a refining aid is incorporated into the molten metal.
  • these additives have an important role in reducing the oxygen content.
  • the steelmaker perfectly controls the flowability of the metal, through the calibrated pouring orifices.
  • the adjuvant also makes it possible to adjust the level of elements such as sulfur, phosphorus under certain conditions of use. A favorable action on the number and morphology of inclusions is obtained. This is particularly the case for inclusions of alumina in processes where the steel has been quenched with aluminum.
  • the addition of calcium inside the liquid mass can be carried out using methods of introducing additives in the form of powder or granules.
  • the presentation EP-A-0 030 043 which insists on the importance of having a particle size as homogeneous as possible.
  • the alloy is in the form of granules and can be binary, ternary or multi-component.
  • the second metallic element is chosen from aluminum, copper, nickel, bismuth, lead, tin, lanthanum and silicon, as well as zinc or magnesium alloys.
  • the refining aid is an alloy in the form of granules, each granule having a substantially spherical shape.
  • the alloy consists of one or more metals preferably chosen from beryllium, magnesium, calcium, strontium, barium and zinc and one or more metallic elements whose composition is located in an area of the diagram phases starting from group IIA metal or pure zinc towards the first eutectic point.
  • first eutectic zone we will speak of "first eutectic zone" since it corresponds to the lowering of the melting point in the direction of a binary or multi-component eutectic. It is therefore an alloy located in the eutectic zone, including the eutectic itself, which will be the refining alloy.
  • alloys of calcium or magnesium with aluminum, copper or nickel As binary alloys, let us advantageously mention the alloys of calcium or magnesium with aluminum, copper or nickel. As ternary alloys, mention will be made, for example, of calcium, nickel, aluminum and calcium, magnesium, aluminum alloys.
  • thermodynamic level or can start from the equation expressing as a first approximation the activity coefficient of an element with high dilution in a solvent, in this case y AT (AT for alkaline- earthy or zinc).
  • the vapor pressure of the metal of group IIA chosen (or of zinc) taken separately is as low as possible; the metals chosen for the alloy form defined compounds with free enthalpy of very negative formation with which at eutectic temperature the eutectic alloy is in equilibrium.
  • the addition of the alloy into granules is done by conventional techniques of deep introduction at the level of the molten metal bath, the granules being substantially spherical, calibrated, constant and homogeneous. Their micro-structure is closed and their diameter is between 0.1 and 2.5 mm, preferably between 0.2 and 2.5 mm. This finely divided form is free from fine particle size dust; this gives the product complete safety in use; thus any danger of explosion or self-ignition due to the pyrophoricity of the reactive alloys is eliminated.
  • the invention also provides major advantages in the production of these granulated alloys. Indeed, in the case of their granulation in the liquid phase, it is possible to work at a lower temperature and to make serious energy savings.
  • the range of steels which benefit from being refined according to the invention using granules of alloys of metals of group IIA and the abovementioned metals are in particular steels with a very low content of residual elements such as carbon and silicon , for example the range of steels for deep drawing.
  • the adjuvant granules are also very suitable for refining other ranges of steels such as stainless steels.
  • non-ferrous metal metals and aluminum can be refined, for example by granules of strontium and aluminum alloys, optionally comprising lithium.
  • the calcium alloy with nickel can contain up to 16 atomic% of nickel, ie approximately 20% by weight.
  • the calcium melts around 850 ° C. and forms with nickel an eutectic alloy melting at approximately 605 ° C., corresponding precisely to the 16 atomic% mentioned. above.
  • the eutectic zone is therefore the zone located on the left of the diagram and extending up to 16 atomic% of nickel alloyed with calcium, including the eutectic itself.
  • compositions of between 5% (fusion around 800 ° C.) and 16 atomic% of nickel are chosen.
  • the Ca / Ni alloy can be added to the steel at a rate of 150 ppm per minute, an addition rate that cannot be kept with pure calcium.
  • the steel obtained appears, on analysis, to have the following composition:
  • the ternary Ca / Mg / AI alloy of Example 6 is used in particular for the treatment of lead, owing to its low melting point and to an increased dissolution rate. It is found that this alloy is of great interest for the debismutage of lead.
  • the Ca / Cu alloy of Example 7 can be used for the treatment of bronze, given its low melting point and the reduced bubbling it causes.
  • the Ca / La alloy of Example 8 can be used for the treatment of steels and cast irons, where, in addition to the reduced bubbling which it causes, it allows very good desulphurization and very fine control of the graphitization.
  • the Mg / Ni alloy of Example 9 can be used for the treatment of stainless steels, its melting point being particularly low. It causes reduced boiling, just like the Ca / Ni alloys of Examples 1 to 3.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Manufacture And Refinement Of Metals (AREA)
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Abstract

The refining additive is an alloy in the form of granules of a metal selected from the group of alkaline earth metals and zinc with a small quantity of a metallic element capable of giving the alloy a substantially lower melting point. The alloy can be a eutectic alloy. This alloy, which is in the form of granules, allows the treatment of steels, cast iron and non-ferrous metals at lower temperatures and with a substantial reduction in bubble formation. The alloy may be introduced in the form of a core wire.

Description

La présente invention se rapporte à un procédé de traitement des métaux et alliages, plus particulièrement mais non exclusivement des métaux et alliages ferreux, notamment ceux ayant un haut point de fusion, par exemple supérieur à 1000°C.The present invention relates to a process for the treatment of metals and alloys, more particularly but not exclusively of ferrous metals and alloys, in particular those having a high melting point, for example greater than 1000 ° C.

Pour ce faire, on incorpore au métal en fusion un adjuvant d'affinage.To do this, a refining aid is incorporated into the molten metal.

L'élaboration, la mise à la nuance d'affinage des masses métalliques liquides et en particulier certaines fabrications de l'acier nécessite l'apport d'additifs devant se présenter sous forme pulvérulente.The development, the refining nuance of liquid metallic masses and in particular certain steel manufacturing requires the addition of additives which must be in powder form.

Dans la gamme des aciers destinés à être coulés en continu, ces additifs ont un rôle important pour diminuer la teneur en oxygène. Par ce contrôle de l'oxygène total, l'aciériste maîtrise parfaitement la coulabilité du métal, à travers les orifices calibrés de coulée. L'adjuvant permet par ailleurs de régler le niveau d'éléments tels que soufre, phosphore sous certaines conditions d'emploi. Une action favorable sur le nombre et la morphologie des inclusions est obtenue. C'est le cas notamment des inclusions d'alumine dans les procédés où l'acier a été calmé à l'aluminium.In the range of steels intended for continuous casting, these additives have an important role in reducing the oxygen content. By this total oxygen control, the steelmaker perfectly controls the flowability of the metal, through the calibrated pouring orifices. The adjuvant also makes it possible to adjust the level of elements such as sulfur, phosphorus under certain conditions of use. A favorable action on the number and morphology of inclusions is obtained. This is particularly the case for inclusions of alumina in processes where the steel has been quenched with aluminum.

Depuis plusieurs années, on s'est mis à utiliser le calcium comme adjuvant d'affinage. Le calcium métal présente de nombreux avantages et son efficacité est d'autant plus importante que l'addition est fractionnée et contrôlée dans le temps. L'influence d'une addition de calcium dans l'acier liquide sur les teneurs en oxygène, en soufre, en phosphore, dans un bain d'acier, est parfaitement connue.For several years, calcium has been used as a refining aid. Calcium metal has many advantages and its effectiveness is all the more important as the addition is fractionated and controlled over time. The influence of an addition of calcium in liquid steel on the oxygen, sulfur, phosphorus contents in a steel bath is well known.

L'adjonction de calcium à l'intérieur de la masse liquide peut s'effectuer à l'aide de procédés d'introduction d'additifs sous forme de poudre ou de granules. A ce sujet on retiendra l'exposé EP-A-0 030 043 qui insiste sur l'importance d'avoir une granulométrie aussi homogène que possible.The addition of calcium inside the liquid mass can be carried out using methods of introducing additives in the form of powder or granules. On this subject, note the presentation EP-A-0 030 043 which insists on the importance of having a particle size as homogeneous as possible.

En ce qui concerne la granulation du calcium et la préparation du calcium granulé, on se référera avantageusement à l'exposé d'invention FR-A-2 471 827=WO-A-81/01811 qui mentionne l'utilisation de calcium en général et de calcium granulé en particulier comme adjuvant d'affinage des fontes et aciers.With regard to the granulation of calcium and the preparation of granulated calcium, reference will advantageously be made to the description of the invention FR-A-2 471 827 = WO-A-81/01811 which mentions the use of calcium in general and granulated calcium in particular as an adjuvant for refining cast irons and steels.

L'inconvénient de l'affinage au calcium pur est que ce métal est très réactif et présente une grande tension de vapeur aux températures habituelles de traitement de la masse liquide. L'introduction de calcium entraîne un bouillonnement tel que l'on est souvent obligé de l'employer avec des éléments de dilution, par exemple des composés d'oxydes d'aluminate de calcium, de Spath fluor ou de chaux.The disadvantage of refining with pure calcium is that this metal is very reactive and has a high vapor pressure at the usual temperatures for treating the liquid mass. The introduction of calcium causes boiling such that it is often forced to use it with diluting elements, for example compounds of calcium aluminate oxides, fluorspar or lime.

Selon l'invention, on utilise, comme adjuvant d'affinage, un alliage d'un premier métal choisi parmi les métaux du groupe IIA de la classification périodique, et le zinc, avec un second élément métallique en proportions susceptible de conférer à l'alliage un point de fusion plus bas que celui du premier métal. L'alliage se présente sous forme de granules et peut être binaire, ternaire ou à multi-composants.According to the invention, an alloy of a first metal chosen from the metals of group IIA of the periodic table, and zinc, with a second metallic element in proportions capable of giving the alloy a lower melting point than that of the first metal. The alloy is in the form of granules and can be binary, ternary or multi-component.

Le second élément métallique est choisi parmi l'aluminium, le cuivre, le nickel, le bismuth, le plomb, l'etain, le lanthane et le silicium, ainsi que les alliages de zinc ou de magnésium.The second metallic element is chosen from aluminum, copper, nickel, bismuth, lead, tin, lanthanum and silicon, as well as zinc or magnesium alloys.

En d'autres termes, l'adjuvant d'affinage est un alliage sous forme de granules, chaque granule ayant une forme sensiblement sphérique. L'alliage est constitué d'un ou de plusieurs métaux choisis de préférence parmi le béryllium, le magnésium, le calcium, le strontium, le baryum et le zinc et de un ou plusieurs éléments metalliques dont la composition se situe dans une zone du diagramme des phases partant du métal du groupe IIA ou du zinc pur en direction du premier point eutectique. Pour faire référence à cette zone, on parlera de "première zone eutectique" puisqu'elle correspond à l'abaissement du point de fusion en direction d'un eutectique binaire ou à multiples composants. C'est donc un alliage se situant dans la zone eutectique, y compris l'eutectique lui-méme, qui sera l'alliage d'affinage.In other words, the refining aid is an alloy in the form of granules, each granule having a substantially spherical shape. The alloy consists of one or more metals preferably chosen from beryllium, magnesium, calcium, strontium, barium and zinc and one or more metallic elements whose composition is located in an area of the diagram phases starting from group IIA metal or pure zinc towards the first eutectic point. To refer to this zone, we will speak of "first eutectic zone" since it corresponds to the lowering of the melting point in the direction of a binary or multi-component eutectic. It is therefore an alloy located in the eutectic zone, including the eutectic itself, which will be the refining alloy.

Comme alliages binaires, citons avantageusement les alliages de calcium ou de magnésium avec l'aluminium, le cuivre ou le nickel. Comme alliages ternaires, on citera, par exemple, les alliages calcium, nickel, aluminium et calcium, magnésium, aluminium.As binary alloys, let us advantageously mention the alloys of calcium or magnesium with aluminum, copper or nickel. As ternary alloys, mention will be made, for example, of calcium, nickel, aluminum and calcium, magnesium, aluminum alloys.

On s'est aperçu de façon tout-à-fait inattendue que la présence d'un des métaux de la catégorie ci-dessus conduisait à un abaissement très important du bouillonnement, lors de l'introduction de l'adjuvant de traitement. Ceci s'explique par une baisse importante de la tension de vapeur de l'adjuvant allié par rapport à un adjuvant pur, et par le contrôle parfait de l'écoulement de cet adjuvant pendant son introduction dans le métal à traiter, grâce à sa forme sensiblement sphérique.It has been found quite unexpectedly that the presence of one of the metals of the above category leads to a very significant lowering of the boiling, during the introduction of the processing aid. This is explained by a significant drop in the vapor pressure of the alloyed adjuvant compared to a pure adjuvant, and by the perfect control of the flow of this adjuvant during its introduction into the metal to be treated, thanks to its shape. substantially spherical.

Ainsi, dans le cas du calcium allié introduit dans l'acier liquide sous forme de granules, il est possible d'augmenter l'apport continu de cet adjuvant jusqu'à des quantités de 150 ppm par minute, valeurs impossibles à atteindre avec du calcium pur en granules, a fortiori avec du calcium pur non granulé.Thus, in the case of alloyed calcium introduced into liquid steel in the form of granules, it is possible to increase the continuous supply of this adjuvant up to amounts of 150 ppm per minute, values impossible to achieve with calcium pure in granules, a fortiori with pure non-granulated calcium.

Pour tenter d'expliquer ce phénomène sur un plan thermodynamique, ou peut partir de l'équation exprimant en première approximation le coefficient d'activité d'un élément à forte dilution dans un solvant, en l'occurrence yAT (AT pour alcalino-terreux ou zinc).To try to explain this phenomenon on a thermodynamic level, or can start from the equation expressing as a first approximation the activity coefficient of an element with high dilution in a solvent, in this case y AT (AT for alkaline- earthy or zinc).

Rappelons qu'on exprime en première approximation le coefficient d'activité d'un élément tel qu'un alcalino-terreux à forte dilution dans un solvant par une relation du type:

Figure imgb0001
où Y;,T représente le coefficient d'activité AT dans le solvant, par exemple du calcium dans du fer pur, à dilution infinie.

  • XAT représente la fraction atomique de l'alcalino-terreux ou du zinc,
  • x; représente la fraction atomique de l'élément choisi "i", allié à l'alcalino-terreux ou au zinc.
Recall that we express as a first approximation the activity coefficient of an element such as an alkaline earth with high dilution in a solvent by a relation of the type:
Figure imgb0001
 where Y ;, T represents the activity coefficient AT in the solvent, for example calcium in pure iron, at infinite dilution.
  • XAT represents the atomic fraction of alkaline earth or zinc,
  • x ; represents the atomic fraction of the selected element "i", alloyed with alkaline earth or zinc.

La terme e:1T étant fortement négatif, il en résulte un abaissement considérable de l'activité dans le solvant, par exemple le calcium dans l'acier et par conséquent de sa tension de vapeur.The term e : 1 T being strongly negative, this results in a considerable lowering of the activity in the solvent, for example the calcium in the steel and consequently of its vapor pressure.

Avantageusement, la tension de vapeur du métale du groupe IIA choisi (ou du zinc) pris séparément est aussi faible que possible; les métaux choisis pour l'alliage forment des composés définis à enthalpie libre de formation très négativ avec lesquels à la température eutectique l'alliage eutectique se trouve en équilibre.Advantageously, the vapor pressure of the metal of group IIA chosen (or of zinc) taken separately is as low as possible; the metals chosen for the alloy form defined compounds with free enthalpy of very negative formation with which at eutectic temperature the eutectic alloy is in equilibrium.

On précisera en outre qui'il s'agit bien d'un alliage, chaque granule étant en soit un alliage et non d'un mélange statistique des deux métaux.It will also be specified that it is indeed an alloy, each granule being in itself an alloy and not a statistical mixture of the two metals.

Un tel mélange statistique ne conduirait pas à un abaissement du point de fusion ni aux effects inattendus mentionnés ci-dessus. Preuve en est les mélanges calcium, manganèse qui ne forment pas de véritables alliages et ne présentent donc pas d'intérêt pour la mise en oeuvre du procédé selon l'invention.Such statistical mixing would not lead to a lowering of the melting point or to the unexpected effects mentioned above. Proof of this is the calcium and manganese mixtures which do not form real alloys and therefore are not of interest for implementing the method according to the invention.

L'adjonction de l'alliage en granules se fait par les techniques conventionnelles d'introduction profonde au niveau du bain métallique fondu, les granules étant sensiblement sphériques, calibrés, constants et homogènes. Leur micro-structure est fermée et leur diamètre est compris entre 0,1 et 2,5 mm, de préférence entre 0,2 et 2,5 mm. Cette forme finement divisée est exempte de poussières de fine granulométrie; ceci confère au produit une complète sûreté d'emploi; ainsi tout danger d'explosion ou d'auto-inflammation dû à la pyrophoricité des alliages réactifs est écarté.The addition of the alloy into granules is done by conventional techniques of deep introduction at the level of the molten metal bath, the granules being substantially spherical, calibrated, constant and homogeneous. Their micro-structure is closed and their diameter is between 0.1 and 2.5 mm, preferably between 0.2 and 2.5 mm. This finely divided form is free from fine particle size dust; this gives the product complete safety in use; thus any danger of explosion or self-ignition due to the pyrophoricity of the reactive alloys is eliminated.

L'invention apporte également de gros avantages au niveau de la production de ces alliages granulés. En effet, dans le cas de leur granulation en phase liquide, il est possible de travailler à plus basse température et de faire de sérieuses économies d'énergie.The invention also provides major advantages in the production of these granulated alloys. Indeed, in the case of their granulation in the liquid phase, it is possible to work at a lower temperature and to make serious energy savings.

La gamme des aciers qui gagnent à être affinés selon l'invention à l'aide des granules d'alliages des métaux du groupe IIA et des métaux précités sont en particulier des aciers à très basse teneur en éléments résiduels tels que le carbone et le silicium, par exemple la gamme des aciers pour emboutissage profond.The range of steels which benefit from being refined according to the invention using granules of alloys of metals of group IIA and the abovementioned metals are in particular steels with a very low content of residual elements such as carbon and silicon , for example the range of steels for deep drawing.

Les granules d'adjuvant conviennent aussi fort bien à l'affinage d'autres gammes d'aciers tels que le aciers inoxydables.The adjuvant granules are also very suitable for refining other ranges of steels such as stainless steels.

On peut aussi affiner avec ces granules d'autres éléments que l'acier, par exemple la fonte, le ferronickel, le ferro-chrome et le ferro-manganèse, ainsi que le nickel et le cuivre Blister.It is also possible to refine with these granules other elements than steel, for example cast iron, ferronickel, ferro-chromium and ferro-manganese, as well as nickel and copper blister.

On peut enfin affiner des métaux de métaux non ferreux et l'aluminium par exemple par des granules d'alliages de strontium et d'aluminium, comprenant éventuellement du lithium.Finally, non-ferrous metal metals and aluminum can be refined, for example by granules of strontium and aluminum alloys, optionally comprising lithium.

L'invention est illustrée dans les exemples suivants, donnés à titre non limitatif.The invention is illustrated in the following examples, given without limitation.

ExemplesExamples

Figure imgb0002
Figure imgb0002

Examples 1 à 3Examples 1 to 3

L'alliage de calcium avec le nickel peut contenir jusqu'a 16% atomiques de nickel soit environ 20% pondéraux.The calcium alloy with nickel can contain up to 16 atomic% of nickel, ie approximately 20% by weight.

Comme on le voit sur le dessin annexé, figure unique, représentant le diagramme de phase Ca/Ni, le calcium fond vers 850°C et forme avec le nickel un alliage eutectique fondant à 605°C environ, correspondant précisément aux 16% atomiques mentionnés ci-dessus.As can be seen in the attached drawing, a single figure, representing the Ca / Ni phase diagram, the calcium melts around 850 ° C. and forms with nickel an eutectic alloy melting at approximately 605 ° C., corresponding precisely to the 16 atomic% mentioned. above.

La zone eutectique est donc la zone située à gauche du diagramme et s'étendant jusqu'à 16% atomiques de nickel allié au calcium, y compris l'eutectique lui-même.The eutectic zone is therefore the zone located on the left of the diagram and extending up to 16 atomic% of nickel alloyed with calcium, including the eutectic itself.

De préférence, on choisit des compositions comprises entre 5% (fusion vers 800°C) et 16% atomiques de nickel.Preferably, compositions of between 5% (fusion around 800 ° C.) and 16 atomic% of nickel are chosen.

Comme indiqué plus haut, l'alliage Ca/Ni peut être ajouté à l'acier à raison de 150 ppm par minute, taux d'adjonction qu'il n'est pas possible de tenir avec le calcium pur.As indicated above, the Ca / Ni alloy can be added to the steel at a rate of 150 ppm per minute, an addition rate that cannot be kept with pure calcium.

Lors de l'injection on ne note aucune agitation du matériel en surface, et on constate l'excellente propreté du métal et sa parfaite coulabilité en coulée continue.During the injection, there is no agitation of the material on the surface, and we note the excellent cleanliness of the metal and its perfect flowability in continuous casting.

En outre, autre résultat inattendu, on s'est aperçu que la présence de nickel facilite fortement la solubilité du calcium dans certains aciers.In addition, another unexpected result, it has been found that the presence of nickel greatly facilitates the solubility of calcium in certain steels.

On peut expliquer ce phénomène thermodynamiquement car l'interaction Ca/Ni est fortement négative c'est-à-dire que le coefficient d'activité du calcium dans la fer à dilution infinie est fortement abaissé par la présence d'un peu de nickel.We can explain this phenomenon thermodynamically because the Ca / Ni interaction is strongly negative, that is to say that the activity coefficient of calcium in the iron with infinite dilution is strongly lowered by the presence of a little nickel.

Il faut signaler enfin la présence dans l'acier de l'élément additionnant le calcium, c'est-à-dire le nickel, aux taux précités n'est en rien préjudiciable à la qualité de l'acier final. Le nickel dissout totalement et ne représente en ajour comparé qu'une quantité négligeable.Finally, the presence in the steel of the element adding calcium, that is to say nickel, at the abovementioned rates must not be detrimental to the quality of the final steel. Nickel dissolves completely and represents only a negligible amount in open air compared.

Exemples 4 et 5Examples 4 and 5

Ces exemples permettent de montrer les caractéristiques physiques et chimiques de l'alliage sous forme de granules mis en oeuvre sur un acier à très basse teneur en carbone, calmé à l'aluminium, pour la fabrication de tôles pour l'emboutissage profond.These examples make it possible to show the physical and chemical characteristics of the alloy in the form of granules used on a steel with very low carbon content, calmed with aluminum, for the manufacture of sheets for deep drawing.

L'acier à affiner doit avoir la composition suivante:

Figure imgb0003
Les caractéristiques de l'alliage adjuvant sont les suivantes:

  • granules de calcium contenant 5% d'aluminium (exemple 4)
  • quantité injectée = 420 ppm
  • quantité de'acier traité = 152 tonnes
The steel to be refined must have the following composition:
Figure imgb0003
 The characteristics of the adjuvant alloy are as follows:
  • calcium granules containing 5% aluminum (example 4)
  • quantity injected = 420 ppm
  • quantity of steel treated = 152 tonnes

L'acier obtenu se révèle, à l'analyse, avoir la composition suivante:

Figure imgb0004
The steel obtained appears, on analysis, to have the following composition:
Figure imgb0004

Là encore, on note peu de fumée, aucune ignition de matériel en surface, une excellente qualité de propreté du métal et une coulabilité parfaite en coulée continue.Again, there is little smoke, no ignition of material on the surface, excellent cleanliness of the metal and perfect flowability in continuous casting.

Exemples 6 à 9Examples 6 to 9

L'alliage ternaire Ca/Mg/AI de l'exemple 6 sert notamment au traitement du plomb, par suite de son bas point de fusion et d'une vitesse de dissolution augmentée. On constate que cet alliage trouve un grand intérêt pour le débismutage du plomb.The ternary Ca / Mg / AI alloy of Example 6 is used in particular for the treatment of lead, owing to its low melting point and to an increased dissolution rate. It is found that this alloy is of great interest for the debismutage of lead.

L'alliage Ca/Cu de l'exemple 7 peut servir au traitement du bronze, vu son bas point de fusion et le bouillonnment réduit qu'il entraîne.The Ca / Cu alloy of Example 7 can be used for the treatment of bronze, given its low melting point and the reduced bubbling it causes.

L'alliage Ca/La de l'exemple 8 peut servir au traitement des aciers et fontes, où, outre le bouillonnement réduit qu'il entraîne, il permet une très bonne désulfuration et un contrôle très fin de la graphitisation.The Ca / La alloy of Example 8 can be used for the treatment of steels and cast irons, where, in addition to the reduced bubbling which it causes, it allows very good desulphurization and very fine control of the graphitization.

L'alliage Mg/Ni de l'exemple 9 peut servir au traitement des aciers inoxydables, son point de fusion étant particulièrement bas. Il entraîne un bouillonnement réduit, au même titre que les alliages Ca/Ni des exemples 1 à 3.The Mg / Ni alloy of Example 9 can be used for the treatment of stainless steels, its melting point being particularly low. It causes reduced boiling, just like the Ca / Ni alloys of Examples 1 to 3.

Claims (8)

1. A process for treating a metal or alloy which comprises adding thereto, when in a molten state, a refining additive in which the refining additive is an alloy of a first metal selected among the metals of group Ila of the periodic table and zinc, and a second metallic element in proportion capable of giving to the alloy a melting point lower than that of the first metal, the alloy being in the form of granules, characterized in that the second metallic element is selected among aluminium, copper, nickel, bismuth, lead, tin, lanthanum and silicon, as well as alloys of zinc or of magnesium.
2. A process according to claim 1, characterized in that the refining alloy to be added is a eutectic alloy.
3. A process according to claim 1, characterized in that the refining alloy to be added is an alloy situated in the first eutectic zone, comprised between the melting points of the first metal and of the first eutectic encountered.
4. A process according to claim 1, characterized in that the refining alloy to be added is an alloy of calcium and nickel containng up to 16% atomic of nickel.
5. A process according to claim 1, characterized in that the refining alloy to be added is an alloy of magnesium and nickel containing up to 11.3% atomic of nickel.
6. A process according to claim 4, characterized in that the refining alloy is added at rates up to 150 ppm per minute.
7. A process according to claim 6, characterized in that the grain size of the refining alloy to be added is from 0.1 to 2.5 mm.
8. Use of the process according to one of claims 1 to 7 for refining steels with a low content of carbon, silicon or residual elements, stainless steels or highly alloyed steels and cast iron.
EP85905413A 1984-11-05 1985-10-30 Method for the treatment of metals and alloys for the refining thereof Expired - Lifetime EP0233872B1 (en)

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ES8701850A1 (en) 1987-01-01
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NO862699L (en) 1986-07-03
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PT81432A (en) 1985-12-01
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