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EP0190089A1 - Verfahren zum Behandeln von flüssigen Metallen mittels eines kalziumenthaltenden Fülldrahtes - Google Patents

Verfahren zum Behandeln von flüssigen Metallen mittels eines kalziumenthaltenden Fülldrahtes Download PDF

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Publication number
EP0190089A1
EP0190089A1 EP86420021A EP86420021A EP0190089A1 EP 0190089 A1 EP0190089 A1 EP 0190089A1 EP 86420021 A EP86420021 A EP 86420021A EP 86420021 A EP86420021 A EP 86420021A EP 0190089 A1 EP0190089 A1 EP 0190089A1
Authority
EP
European Patent Office
Prior art keywords
cored wire
calcium
mass
alloy
basic constituent
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.)
Granted
Application number
EP86420021A
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English (en)
French (fr)
Other versions
EP0190089B1 (de
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/de
Application granted granted Critical
Publication of EP0190089B1 publication Critical patent/EP0190089B1/de
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. of which is housed matter 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 60X by mass of Si and experience has shown that it is hardly possible to significantly enrich this Ca alloy beyond 40X. While only about 15X of the Ca introduced into the steel remains fixed there, the Si, on the contrary, is entirely fixed.
  • the steel is therefore enriched with 250 to 1200 ppm 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 It is therefore not possible to respect it if an Si-Ca alloy is used as the core of a cored wire introduced into a like steel.
  • European patent application 30043 describes a process 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 974835 also proposes the deoxidation of cast irons and steels by reactive metals such as Al, 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 vapor pressure. high of metals such as Ca or Mg at the temperature of a bath of liquid steel.
  • German patent 1220617 a treatment alloy is proposed which makes it possible to obtain fine grain steels.
  • This alloy contains from 5 to 40X of Ca, 5 to 55X of one or more elements of the group comprising Al, 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 12.7X - Ca 20.5% - Si 45.7% - Mg 4.5%.
  • the second contains: Fe 33.5% - Ca. 29.5% - Si 36%.
  • 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) under a mild steel sheath.
  • bastnaesite Ca and La fluocarbonate
  • 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 of preparing a metal or metallic alloy in the liquid state, preferably subjecting it, beforehand, to deoxidation, then introducing into the metallic bath formed a cored wire whose core contains a material of which the constituent base is an alloy whose calcium content is at least 75% by mass, an alloy also containing at least one metal from the group comprising nickel and aluminum, the total content of this alloy of nickel plus aluminum being at least equal to 5% by mass.
  • This alloy can contain various impurities and / or additional additions.
  • the calcium content of the alloy is at least 80X by mass, the nickel plus aluminum content in this case being 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 alloy, an essential basic constituent of the material which forms the core of the cored wire represents at least 30% by mass of the total weight of this material.
  • This material can also, for certain applications, contain another alloy comprising calcium, such as a silico-calcium.
  • It can also contain elements, metallic or not, in alloyed or unalloyed 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 basic constituent of 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 take place, for example, in a ladle and / or in a distributor in the case of continuous casting.
  • 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 point of view of the silicon content, 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 making it possible to treat a liquid metal or alloy, in particular a steel, the core of which preferably contains a material in divided form, that is to say pulverulent or granular, compacted or not, the constituent of which is base is an alloy containing at least 75X by mass of calcium and at least one metal from the group comprising nickel and aluminum, the total content of this alloy of nickel plus aluminum being at least equal to 5% by mass.
  • Figure 1 is a diagram of a device for evaluating the intensity of the boiling of the liquid steel caused by the introduction of a cored wire containing calcium.
  • Figure 2 is a detail of Figure 1 seen along the arrow (F).
  • FIG. 3 is a diagram which shows the relationship between the speed of introduction of the cored wire and the intensity of the boiling of the liquid steel.
  • FIG. 1 represents a pocket (1) containing 83 tonnes of liquid steel (2).
  • At a distance (H) of 300mm from the surface of the slag are located 16 cups, such as (4), made of steel, of approximately 50mm in diameter suspended below a steel disc (5) of 1.2m in diameter itself hanging above the pocket.
  • 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 diagrammatically 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 0.4mm thick and a rectangular section of 16 by 7.5mm.
  • the core of this cored wire is a divided material consisting of a CaNi alloy containing 87Z 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 Figure 3 separates a -lower zone for which, out of 19 tests, only 1 causes 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 dividing line can be drawn between a lower zone for which the vast majority of the results do not give rise to too intense bubbling and an upper zone for which this bubbling becomes too violent.
  • This separation line corresponds to a speed of introduction of the cored wire of 120 m / min.
  • This wire containing 180g of SiCa alloy per meter, the maximum rate of Ca introduction is therefore in this case 78g per ton per minute.
  • the analyzes carried out show that the yield of calcium introduction is, in the case of the Si Ca alloy of 15 X on average.
  • the silicon introduction yield is practically 100%.
  • 360 ppm of silicon is fixed.
  • Such an addition is incompatible with the development 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% Si 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 at 30% Ca and 60% Si.
  • This invention also relates to the cored wire.
  • the envelope of this wire can, in particular, be made of steel or any metal compatible with the bath to be treated.

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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)
  • ing And Chemical Polishing (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Wire Processing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP86420021A 1985-01-24 1986-01-22 Verfahren zum Behandeln von flüssigen Metallen mittels eines kalziumenthaltenden Fülldrahtes Expired EP0190089B1 (de)

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
FR8501331 1985-01-24
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

Publications (2)

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

Family

ID=26224355

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86420021A Expired EP0190089B1 (de) 1985-01-24 1986-01-22 Verfahren zum Behandeln von flüssigen Metallen mittels eines kalziumenthaltenden Fülldrahtes

Country Status (6)

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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2154676C1 (ru) * 1999-11-16 2000-08-20 Московский государственный вечерний металлургический институт Способ изготовления рафинирующей добавки
WO2001042517A1 (de) * 1999-12-06 2001-06-14 Firma Caltex Gmbh Verfahren zur herstellung von injektionsdraht
RU2218421C1 (ru) * 2002-03-07 2003-12-10 Московский государственный вечерний металлургический институт Способ легирования стали
EP1715065A2 (de) * 2005-04-20 2006-10-25 Corus Staal BV Fülldraht zur Behandlung von Stahlschmelzen mittels Drahtinjektion
RU2443785C1 (ru) * 2010-09-27 2012-02-27 Закрытое акционерное общество "ФЕРРОСПЛАВ" Наполнитель порошковой проволоки для внепечной обработки металлургических расплавов
WO2014009327A1 (de) * 2012-07-10 2014-01-16 DÖRING-FREISSMUTH, Mechthilde Fülldraht und verfahren zur behandlung von eisen- oder stahlschmelzen

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2145358C1 (ru) * 1998-08-20 2000-02-10 Белорусский Металлургический Завод Способ внепечной обработки стали
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
RU2151199C1 (ru) * 1999-08-25 2000-06-20 ОАО "Завод "Универсальное оборудование" Способ внепечной обработки стали
RU2337144C1 (ru) * 2007-02-07 2008-10-27 Юрий Васильевич Суетин Проволока для внепечной обработки металлургических расплавов
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
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

Citations (4)

* 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
DE2421743A1 (de) * 1974-05-06 1975-11-20 Ototani Tohei Umkleidete calciumkoerper zum desoxidieren und entschwefeln von eisen- und stahlschmelzen u. dgl.
EP0030043A2 (de) * 1979-12-04 1981-06-10 Metallgesellschaft Ag Drahtförmiges Mittel zum Behandeln von Metallschmelzen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4828279A (en) * 1978-07-12 1980-01-17 Lava Crucible-Refractories Co. Introducing agents into a vessel of molten metal
ATE12260T1 (de) * 1980-07-09 1985-04-15 Foseco Int Metallurgische behandlungsmittel.
EP0137618B1 (de) * 1983-08-12 1988-06-22 Pfizer Inc. Verfahren und Vorrichtung zum Einbringen von Calcium in Eisenschmelzen

Patent Citations (4)

* 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
DE2421743A1 (de) * 1974-05-06 1975-11-20 Ototani Tohei Umkleidete calciumkoerper zum desoxidieren und entschwefeln von eisen- und stahlschmelzen u. dgl.
EP0030043A2 (de) * 1979-12-04 1981-06-10 Metallgesellschaft Ag Drahtförmiges Mittel zum Behandeln von Metallschmelzen

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2154676C1 (ru) * 1999-11-16 2000-08-20 Московский государственный вечерний металлургический институт Способ изготовления рафинирующей добавки
WO2001042517A1 (de) * 1999-12-06 2001-06-14 Firma Caltex Gmbh Verfahren zur herstellung von injektionsdraht
RU2218421C1 (ru) * 2002-03-07 2003-12-10 Московский государственный вечерний металлургический институт Способ легирования стали
EP1715065A2 (de) * 2005-04-20 2006-10-25 Corus Staal BV Fülldraht zur Behandlung von Stahlschmelzen mittels Drahtinjektion
RU2443785C1 (ru) * 2010-09-27 2012-02-27 Закрытое акционерное общество "ФЕРРОСПЛАВ" Наполнитель порошковой проволоки для внепечной обработки металлургических расплавов
WO2014009327A1 (de) * 2012-07-10 2014-01-16 DÖRING-FREISSMUTH, Mechthilde Fülldraht und verfahren zur behandlung von eisen- oder stahlschmelzen

Also Published As

Publication number Publication date
EP0190089B1 (de) 1989-01-18
ES8801386A1 (es) 1988-01-01
ATE40154T1 (de) 1989-02-15
DE3661841D1 (en) 1989-02-23
ES556978A0 (es) 1988-01-01
WO1986004359A1 (fr) 1986-07-31
AU5353886A (en) 1986-08-13
AU587228B2 (en) 1989-08-10

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