EP0190089B1 - Procédé de traitement de métaux liquides par fil fourre contenant du calcium - Google Patents

Procédé de traitement de métaux liquides par fil fourre contenant du calcium Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
alloy
cored wire
calcium
mass
core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86420021A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0190089A1 (fr
Inventor
Pierre Boussard
André Gueussier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vallourec SA
Original Assignee
Vallourec SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR8501331A external-priority patent/FR2576320B1/fr
Application filed by Vallourec SA filed Critical Vallourec SA
Priority to AT86420021T priority Critical patent/ATE40154T1/de
Publication of EP0190089A1 publication Critical patent/EP0190089A1/fr
Application granted granted Critical
Publication of EP0190089B1 publication Critical patent/EP0190089B1/fr
Expired legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • 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 & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)
  • ing And Chemical Polishing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Wire Processing (AREA)
EP86420021A 1985-01-24 1986-01-22 Procédé de traitement de métaux liquides par fil fourre contenant du calcium Expired EP0190089B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86420021T ATE40154T1 (de) 1985-01-24 1986-01-22 Verfahren zum behandeln von fluessigen metallen mittels eines kalziumenthaltenden fuelldrahtes.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8501331A FR2576320B1 (fr) 1985-01-24 1985-01-24 Procede de traitement de metaux ferreux liquides par fil fourre contenant du calcium
FR8501332 1985-01-24
FR8501332 1985-01-24
FR8501331 1985-01-24

Publications (2)

Publication Number Publication Date
EP0190089A1 EP0190089A1 (fr) 1986-08-06
EP0190089B1 true EP0190089B1 (fr) 1989-01-18

Family

ID=26224355

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86420021A Expired EP0190089B1 (fr) 1985-01-24 1986-01-22 Procédé de traitement de métaux liquides par fil fourre contenant du calcium

Country Status (6)

Country Link
EP (1) EP0190089B1 (es)
AT (1) ATE40154T1 (es)
AU (1) AU587228B2 (es)
DE (1) DE3661841D1 (es)
ES (1) ES8801386A1 (es)
WO (1) WO1986004359A1 (es)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE512574C2 (sv) * 1998-08-25 2000-04-03 Partek Nordkalk Ab Långsträckt produkt som är verksam vid nedsänkning i ett bad av smält stål för svavelrening
RU2152834C1 (ru) * 1999-12-06 2000-07-20 Неретин Александр Алексеевич Способ изготовления кальциевой проволоки
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 (zh) * 2010-08-19 2010-12-08 谢应凯 用于炼钢的铁包铝钙合金及其制备方法
RU2443785C1 (ru) * 2010-09-27 2012-02-27 Закрытое акционерное общество "ФЕРРОСПЛАВ" Наполнитель порошковой проволоки для внепечной обработки металлургических расплавов
DE102012013662A1 (de) * 2012-07-10 2014-01-16 Mechthilde Döring-Freißmuth Füllldraht und Verfahren zur Behandlung von Eisenschmelzen
CN106350703B (zh) * 2015-07-16 2018-07-10 东北大学 一种用电解原铝液熔盐热还原制备铝钙合金的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE974835C (de) * 1951-02-27 1961-05-10 Max Planck Inst Eisenforschung Verfahren zum Desoxydieren von Eisen- und Stahlschmelzen
DE1220617B (de) * 1958-02-03 1966-07-07 Res Inst Iron Steel Vorlegierung fuer die Herstellung von feinkoernigen Staehlen
DE2421743B2 (de) * 1974-05-06 1979-06-07 Ototani, Tohei, Sendai (Japan) Verfahren zum Herstellen eines stangenförmigen Desoxydations- und Entschwefelungsmittels für Eisen- oder Stahlschmelzen o.dgl
AU4828279A (en) * 1978-07-12 1980-01-17 Lava Crucible-Refractories Co. Introducing agents into a vessel of molten metal
DE2948636A1 (de) * 1979-12-04 1981-06-11 Metallgesellschaft Ag, 6000 Frankfurt Drahtfoermiges mittel zum behandeln von metallschmelzen
EP0044183B1 (en) * 1980-07-09 1985-03-20 Foseco International Limited Metallurgical treatment agents
DE3472274D1 (en) * 1983-08-12 1988-07-28 Pfizer Process and apparatus for adding calcium to a bath of molten ferrous material

Also Published As

Publication number Publication date
AU587228B2 (en) 1989-08-10
ES8801386A1 (es) 1988-01-01
ES556978A0 (es) 1988-01-01
WO1986004359A1 (fr) 1986-07-31
DE3661841D1 (en) 1989-02-23
ATE40154T1 (de) 1989-02-15
AU5353886A (en) 1986-08-13
EP0190089A1 (fr) 1986-08-06

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