EP1811051B1 - Alliage permettant de modifier de la fonte - Google Patents

Alliage permettant de modifier de la fonte Download PDF

Info

Publication number
EP1811051B1
EP1811051B1 EP04808959A EP04808959A EP1811051B1 EP 1811051 B1 EP1811051 B1 EP 1811051B1 EP 04808959 A EP04808959 A EP 04808959A EP 04808959 A EP04808959 A EP 04808959A EP 1811051 B1 EP1811051 B1 EP 1811051B1
Authority
EP
European Patent Office
Prior art keywords
alloy
mass
iron
magnesium
calcium
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.)
Not-in-force
Application number
EP04808959A
Other languages
German (de)
English (en)
Other versions
EP1811051A4 (fr
EP1811051A1 (fr
Inventor
Ivan Vasilievich Ryabchikov
Alexey Gennadyevich Panov
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.)
Dynin Anton Yakovlevich
Original Assignee
Dynin Anton Yakovlevich
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
Application filed by Dynin Anton Yakovlevich filed Critical Dynin Anton Yakovlevich
Publication of EP1811051A1 publication Critical patent/EP1811051A1/fr
Publication of EP1811051A4 publication Critical patent/EP1811051A4/fr
Application granted granted Critical
Publication of EP1811051B1 publication Critical patent/EP1811051B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C21C1/10—Making spheroidal graphite cast-iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/20—Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00

Definitions

  • the invention belongs to the field of "metallurgy” or to the production of a refined and modified alloy for cast iron pieces and their quality improvement.
  • the alloy according to the invention can be used both in iron and steelworks as well as in foundries.
  • the disadvantage of the alloy is a low, spheroidizing and unstable graphitizing ability in the processing of structural gray cast during its manufacture with a wall thickness of at least 3 mm, which degrades the mechanical properties and gives rise to whitening of the cast.
  • the lack of stability of the graphitizing ability is due to a strong dependence of the graphitizing effect of the active element strontium, even with small variations of the content of this element in the alloy of aluminum and calcium. Only rare earth metals in the stated amount without the main spheroidizing element magnesium do not allow the production of graphite in globular form.
  • WO 99/29911 discloses an alloy suitable for the production of spheroidal cast iron consisting of 40-80 Si, 0.5 -10 Ca and / or Sr and / or Ba, 0-10 Ce and / or La, 0-5 Mg, 0-5 Al, 0 -10 Mn and / or Ti and / or Zr, 0.5-10 oxygen in the form of metal oxide 0.1-10 sulfur in the form of metal sulphide, remainder iron.
  • the USSR No. 1813113 (“Cast Iron Modifier", 1993) discloses a modifier for cast iron which is particularly close to the subject of the application in terms of technical properties and the effect to be achieved. This modifier has the following components (the amount is given in%): silicon 15-90 strontium 0.1-10 calcium less than 0.1 Zirconium and / or titanium 0.3-10 iron rest
  • the disadvantage of the modifier is that no modifying effect occurs in the cast iron processing.
  • a content of calcium in the modifier of less than 0.1%, with the lower limit of the silicon content (15%) and with any combination of zirconium and / or titanium in the stated amounts, the solubility limit of strontium is less than 0.1% ( JA Ageew, SA Artschugow, "Investigation of the solubility of alkaline earth metals in molten iron and in alloys contained in molten iron", Zeitschrift für Physikische Chemie, T. LIX 4, 1985, pp. 838-841 ).
  • This modifier can not guarantee a casting with a wall thickness of less than 3 mm from the construction gray cast without brightening.
  • the absence of the spheroidizing component in the modifier also allows the emergence of plate graphite.
  • the object of the present invention is to provide an alloy whose components guarantee a production of cast iron with high hardness and plasticity properties without brightening in the section of iron pieces of less than 3 mm and which also ensures the necessary reproduction of the modified effect.
  • the alloy additionally comprises magnesium and rare earth metals with the following ratio of the components (the amount is given in%): silicon 45-78 magnesium 0.1-7.0 rare earth metals 0.1 to 2.2 strontium 0.1-2.0 calcium 0.1-1.5 aluminum 0.3-2.0 zirconium 0.1-2.0 iron rest
  • magnesium and rare earth metals allow the inclusion of graphite in spherical form, which increases the hardness and plasticity of the cast iron.
  • alloy simultaneously magnesium and zirconium their joint action strengthens the graphitizing effect and reduces whitening in the casting.
  • the ratio of the constituents in the alloy according to the invention is selected so that the joint action of said elements guarantees a reliable reproduction of the modification results. This effect is achieved even with a penetration of production slags into the alloy up to a proportion of 1.0%, whereby these slags arise from oxides and sulfides of metals, and up to a portion of 1.0% of the inactive metals, which as Accompanying substances occur in the layer.
  • the upper and lower limits of the content of alloy components are selected according to the object and the economic reasons.
  • the lower limit of the silicon content in the alloy is due to the fact that with a content of less than 45%, the modifying properties of this element are hardly recognizable.
  • silicon is a solvent for the other alloy component.
  • An increase in the silicon content of more than 78% is not expedient, because this does not lead to a further increase in the modifying ability of this element, but to the increase in value of the alloy.
  • the rare earth metals are introduced into the alloy for the stabilization of the results of the spheroidizing modification because of the neutralization of the admixture of the non-ferrous metal diffusers (Pb, Sn, Sb and others) by their coupling with the finely dispersed compound, which are also additional graphitization centers.
  • High density sulphides and oxysulphides of high density rare earth metals which are comparable to the density of molten iron, also serve as crystallization centers of graphite, thereby strengthening the graphitizing effect. At a content of less than 0.1% in the alloy, its effect on the cast iron properties is little noticeable.
  • a content of rare earth metals higher than 2.2% is impractical because of the alleviation of the increase in the graphitizing ability of these metals and the increase in the cost of the alloy.
  • the individual rare earth metals are lanthanum and neodymium.
  • strontium into the alloy leads to an improvement of the graphite form and to a sudden increase in the graphitizing ability of the strontium. But the graphitizing potential of strontium decreases significantly in the presence of calcium and aluminum.
  • the lower limit of the content of strontium in the alloy is due to the fact that with a proportion of at least 0.1% Sr in this alloy, the addition of this alloy in the cast iron is less effective.
  • the upper limit of the strontium content in the alloy is limited by the possibilities of the alloying operation.
  • the presence of calcium and magnesium in the alloy promotes improvement in the conditions of formation of the graphite nuclei upon crystallization of the cast iron, and the greater the calcium content, the more magnesium the alloy should contain. With a content of calcium of 0.1%, the alloy should contain at most 0.15% magnesium. The upper limit of the content of calcium (1.5%) also corresponds to the upper limit of the magnesium content (7.0%) in the alloy. A calcium content of more than 1.5% in the alloy promotes a reduction in the dissolution rate in the molten cast iron due to the barrier of the attack surface with the resulting silicates.
  • the aluminum content should be at most 2.0%, because aluminum lowers the graphitizing ability of strontium.
  • the lower limit of aluminum in the alloy is explained by a large consumption associated with the refining of ferrosilicon from aluminum because the industrial grades of ferrosilicon contain 2.5% aluminum.
  • magnesium in the alloy in an amount of less than 0.1% disturbs the stabilization of the constituents of the alloy and does not guarantee the necessary content of strontium, calcium and aluminum within narrow limits.
  • the magnesium increases the strontium solubility in the iron-pebble-like melt and makes it possible to keep the content of this element stable at the upper limit (2.0%) even with a minimum content of silicon.
  • magnesium is a important, spheroidizing element. A magnesium content of more than 7% in the alloy leads to increased burnup of the alloy and a pyro effect in the introduction of the modifier into the liquid cast iron. Therefore, this content of magnesium in the alloy is not economically and ecologically appropriate.
  • Zirconium is entered into alloy for leveling harmful effects of aluminum on the graphitizing influence of strontium.
  • the lower limit of the zirconium content corresponds to the lower limit of the content of aluminum in the alloy
  • the upper limit of the zirconium content corresponds to the largest amount of the aluminum in the alloy.
  • the zirconium introduced into the alloy in the specified amount stabilizes the high-performance graphitizing ability of strontium due to the formation of the solid compounds ZrAl 2 , ZrAl 3 and others and gives the possibility of eliminating lightening in thin-walled casting.
  • a zirconium content of less than 0.1% in the alloy does not guarantee a stable action of strontium when the alloy contains 0.3% aluminum. If there is 2.0% zirconium in the alloy, the harmful effect of the aluminum, even if its content is 2.0%, can be avoided.
  • the alloy (Table 1) is made in an induction furnace IST 1.0) in the alloy of silicon, steel scrap, misch metal or phonanium oxide, magnesium, silicozirconium and strontium carbonate. The melt is poured in block form. After cooling, the alloy is separated from the slag and with a jaw crusher (DLSC 80) broken, the fractions have a diameter of 1-5 mm.
  • Table 1 elements Mass fraction of the elements Known salary Content according to the invention 1 2 3 4 5 6 7 * silicon 15 50 90 78 45 77 50 rare earth metals - - - 0.1 0.3 (La) 2.2 1.5 strontium 0.1 5 0.1 0.8 0.1 0.8 2.0 calcium 0.05 0.05 0.1 0.15 0.4 0.15 1.5 aluminum 0.5 0.5 0.5 0.3 0.8 0.5 2.0 zirconium 10 5 0.3 1.2 0.1 0.1 2.0 magnesium - - - 0.1 5.5 0.3 7.0 iron is missing is missing is missing is missing is missing is missing is missing * The alloy contains slag and foreign matter, 1% of each element.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Claims (5)

  1. Alliage de modification de la fonte, qui contient du silicium, du calcium, de l'aluminium, du zirconium et du fer
    caractérisé
    en ce qu' il contient en plus du magnésium et des métaux de terre rare en le rapport suivant des constituants (la masse est donnée en %) silicium 45 à 78 métaux de terre rare 0,2 à 2,2 strontium 0,1 à 2,0 calcium 0,1 à 1,5 aluminium 0,3 à 2,0 magnésium 0,1 à 7,0 zirconium 0,1 à 2,0 fer restant
  2. Alliage suivant la revendication 1,
    caractérisé
    en ce qu'il contient de 0,1 à 1,0 % de magnésium, de 0,1 à 0,2 % de calcium, de 0,3 à 0,5 % d'aluminium et, 0,1 à 0,3 % de métaux de terre rare.
  3. Alliage suivant la revendication 1,
    caractérisé en ce qu'il contient de 4,0 à 7,0 % de magnésium, de 0,2 à 1,0 % de calcium, de 0,5 à 1,5 % d'aluminium, de 0,1 à 0,3 % de zirconium et en ce qu'il est utilisé comme métaux de terre rare des éléments individuels.
  4. Alliage suivant la revendication 3,
    caractérisé en ce qu'il est utilisé comme métaux de terre rare individuels, du lanthane et/ou du néodyme en une proportion représentante de 0,2 à 0,5 % de la quantité totale.
  5. Alliage suivant la revendication 1,
    caractérisé en ce qu'il contient des scories et des substances étrangères à raison de jusqu'à 1% de chaque substance.
EP04808959A 2004-11-04 2004-11-04 Alliage permettant de modifier de la fonte Not-in-force EP1811051B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2004/000435 WO2006049525A1 (fr) 2004-11-04 2004-11-04 Alliage permettant de modifier de la fonte

Publications (3)

Publication Number Publication Date
EP1811051A1 EP1811051A1 (fr) 2007-07-25
EP1811051A4 EP1811051A4 (fr) 2008-01-23
EP1811051B1 true EP1811051B1 (fr) 2008-11-26

Family

ID=36319441

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04808959A Not-in-force EP1811051B1 (fr) 2004-11-04 2004-11-04 Alliage permettant de modifier de la fonte

Country Status (5)

Country Link
EP (1) EP1811051B1 (fr)
AT (1) ATE415499T1 (fr)
DE (1) DE502004008559D1 (fr)
EA (1) EA008521B1 (fr)
WO (1) WO2006049525A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10767238B2 (en) * 2016-04-15 2020-09-08 Elkem Asa Gray cast iron inoculant

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2290273A (en) * 1940-02-07 1942-07-21 Electro Metallurg Co Composition and method for treating cast iron
US3527597A (en) * 1962-08-31 1970-09-08 British Cast Iron Res Ass Carbide suppressing silicon base inoculant for cast iron containing metallic strontium and method of using same
SU739124A1 (ru) * 1978-01-10 1980-06-05 Институт Проблем Литья Ан Украинской Сср Модификатор
JPS5616613A (en) * 1979-07-21 1981-02-17 Toyota Motor Corp Additive for cast iron
DE3824175A1 (de) * 1988-07-16 1990-01-18 Metallgesellschaft Ag Verfahren zur herstellung von gusseisen mit kugelgraphit und/oder vermiculargraphit
SU1723172A1 (ru) * 1990-05-17 1992-03-30 Липецкий Филиал Всесоюзного Проектно-Технологического Института Литейного Производства Модификатор дл чугуна
DE4124159C2 (de) * 1991-07-20 1996-08-14 Sueddeutsche Kalkstickstoff Vorlegierung zur Behandlung von Gußeisenschmelzen
GB9600807D0 (en) * 1996-01-16 1996-03-20 Foseco Int Composition for inoculating low sulphur grey iron
NO306169B1 (no) * 1997-12-08 1999-09-27 Elkem Materials Ympemiddel for stöpejern og fremgangsmÕte for fremstilling av ympemiddel
US6793707B2 (en) * 2002-01-10 2004-09-21 Pechiney Electrometallurgie Inoculation filter

Also Published As

Publication number Publication date
EA008521B1 (ru) 2007-06-29
ATE415499T1 (de) 2008-12-15
EP1811051A4 (fr) 2008-01-23
DE502004008559D1 (de) 2009-01-08
EP1811051A1 (fr) 2007-07-25
WO2006049525A1 (fr) 2006-05-11
EA200501649A1 (ru) 2006-06-30

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