EP1811051B1 - Alloy for modifying iron - Google Patents

Alloy for modifying iron Download PDF

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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
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Prior art keywords
alloy
mass
iron
magnesium
calcium
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German (de)
French (fr)
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EP1811051A4 (en
EP1811051A1 (en
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Ivan Vasilievich Ryabchikov
Alexey Gennadyevich Panov
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Dynin Anton Yakovlevich
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Dynin Anton Yakovlevich
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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
    • 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.

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

Abstract

The invention relates to an alloy for modifying iron containing silicium, strontium, calcium, aluminium, zirconium and iron and additionally containing magnesium and rear-earth metals at a following component ratio: 45-78 mass % silicium, 0.1-2.0 mass % strontium, 0.1-0.15 mass % calcium, 0.3-0.2 mass % aluminium, 0.1-2.0 mass % zirconium, 0.1-7.0 mass % magnesium, 0.1-2.2 mass % rare-earth metals, the rest being iron. An alloy used for iron graphitizing processing contains 0.1-1.0 mass % magnesium, 0.1-0.2 mass % calcium, 0.3-0.5 mass % aluminium and 0.1-0.3 mass % rare-earth metals. An alloy for graphitizing and spheroidizing iron processing contains 4.0-7.0 mass % magnesium, 0.2-1.0 mass % calcium, 0.5-1.5 mass % aluminium, 0.1-0.3 mass % zirconium, rare-earth metals are represented by individual elements in the form of lanthanum and neodymium, wherein the total quantity thereof ranges from 0.2 to 0.5 mass %. The inventive alloy makes it possible to remove chilling on thin-walled casting, increase the iron strength and plasticity and to ensure the modifying effect reproducibility.

Description

Die Erfindung gehört zum Bereich "Metallurgie" beziehungsweise zur Gewinnung einer raffinierten und modifizierten Legierung für Gusseisenstücke und deren Qualitätsverbesserung. Die Legierung gemäß der Erfindung kann sowohl in Eisenhütten- und Maschinenbauwerken als auch in Gießereien verwendet werden.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.

Bekannt ist schon eine Legierung zur Desoxidation und Modifikation von Gusseisen (Erfinderzeugnis der UdSSR Nr. 449979, "Die Legierung zur Desoxidation und Modifikation von Gusseisen", 1974), die Silizium, Seltenerdmetalle, Strontium, Kalzium, Aluminium und Eisen mit dem folgenden Verhältnis der Komponenten enthält (die Menge ist in % gegeben): Silizium 55-80 Seltenerdmetalle 0,1-1,5 Strontium 0,1-5 Kalzium 0,1-5 Aluminium 0,1-3 Eisen Rest Already known is an alloy for the deoxidation and modification of cast iron (invented by USSR No. 449979, "The Alloy for Deoxidation and Modification of Cast Iron", 1974), which comprises silicon, rare earth metals, strontium, calcium, aluminum and iron with the following ratio of Contains components (the amount is given in%): silicon 55-80 rare earth metals 0.1-1.5 strontium 0.1-5 calcium 0.1-5 aluminum 0.1-3 iron rest

Der Nachteil der Legierung ist eine niedrige, sphäroidisierende und nicht stabile graphitisierende Fähigkeit bei der Verarbeitung von Konstruktionsgrauguss bei dessen Herstellung mit einer Wanddichte von mindestens 3 mm, wodurch die mechanischen Eigenschaften verschlechtert werden und eine Aufhellung des Gusses entsteht. Die fehlende Stabilität der graphitisierenden Fähigkeit ist durch eine starke Abhängigkeit der graphitisierenden Wirkung des aktiven Elements Strontium bedingt, sogar bei geringen Schwankungen des Gehalts dieses Elements in der Legierung an Aluminium und Kalzium. Nur Seltenerdmetalle in der genannten Menge ohne das sphäroidisierende Hauptelement Magnesium ermöglichen nicht die Gewinnung von Graphit in globularer Form.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 offenbart eine Legierung geeignet für die Herstellung von Sphärogusseisen, bestehend aus 40-80 Si, 0.5 -10 Ca und/oder Sr und/oder Ba, 0-10 Ce und/oder La, 0-5 Mg, 0-5 Al, 0-10 Mn und/oder Ti und/oder Zr, 0.5-10 Sauerstoff in der Form Metal Oxyd 0.1-10 Schwefel in der Form Metal Sulphide, Rest Eisen. Aus dem Patent der UdSSR Nr. 1813113 ("Gusseisenmodifikator"; 1993) ist ein Modifikator für Gusseisen bekannt, der dem Anmeldungsgegenstand hinsichtlich der technischen Eigenschaften und des zu erreichenden Effekts besonders nahe kommt. Dieser Modifikator weist folgende Komponenten auf (die Menge ist in % gegeben): Silizium 15-90 Strontium 0,1-10 Kalzium weniger als 0,1 Zirkonium und/oder Titan 0,3-10 Eisen Rest 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

Der Nachteil des Modifikators besteht darin, dass keine modifizierende Wirkung bei der Gusseisenverarbeitung entsteht. Bei einem Gehalt an Kalzium im Modifikator von weniger als 0,1 %, bei der Untergrenze des Siliziumgehalts (15 %) und bei einer beliebigen Kombination von Zirkonium und/oder Titan in den angegebenen Mengen beträgt die Lösbarkeitsgrenze von Strontium weniger als 0,1 % ( J. A. Ageew, S. A. Artschugow, "Untersuchung der Lösbarkeit von Erdalkalimetallen im Flüssigeisen und in Legierungen, die im Flüssigeisen enthalten sind", Zeitschrift für physische Chemie, T. LIX 4, 1985, S. 838-841 ). Dieser Modifikator kann nicht einen Guss mit einer Wanddichte von weniger als 3 mm aus dem Konstruktionsgrauguss ohne Aufhellen garantieren. Außerdem ermöglicht das Fehlen der sphäroidisierenden Komponente im Modifikator auch das Entstehen von Plattengraphit.The disadvantage of the modifier is that no modifying effect occurs in the cast iron processing. With 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. In addition, the absence of the spheroidizing component in the modifier also allows the emergence of plate graphite.

Die Aufgabe der vorliegenden Erfindung besteht darin, eine Legierung zu schaffen, deren Bestandteile eine Erzeugung von Gusseisen mit hohen Härte- und Plastizitätseigenschaften ohne Aufhellung im Schnitt von Eisenstücken von weniger als 3 mm garantiert und die auch die notwendige Reproduktion der modifizierten Wirkung gewährleistet.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.

Diese Aufgabe wird dadurch gelöst, dass die Legierung zusätzlich Magnesium und Seltenerdmetalle mit dem folgenden Verhältnis der Komponenten aufweist (die Menge ist in % gegeben): Silizium 45-78 Magnesium 0,1-7,0 Seltenerdmetalle 0,1-2,2 Strontium 0,1-2,0 Kalzium 0,1-1,5 Aluminium 0,3-2,0 Zirkonium 0,1-2,0 Eisen Rest This object is achieved in that 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

Die zusätzliche Einführung von Magnesium und Seltenerdmetallen ermöglicht den Einschluss von Graphit in sphärischer Form, wodurch die Härte und die Plastizität des Gusseisens erhöht werden. Wenn außerdem die Legierung gleichzeitig Magnesium und Zirkonium enthält, stärkt deren gemeinsame Wirkung die graphitisierende Wirkung und mindert die Aufhellung im Guss.The additional introduction of magnesium and rare earth metals allows the inclusion of graphite in spherical form, which increases the hardness and plasticity of the cast iron. In addition, if the alloy simultaneously magnesium and zirconium, their joint action strengthens the graphitizing effect and reduces whitening in the casting.

Das Verhältnis der Bestandteile in der Legierung gemäß der Erfindung ist so ausgewählt, dass die gemeinsame Wirkung der genannten Elemente eine zuverlässige Reproduktion der Modifikationsergebnisse garantiert. Diese Wirkung wird sogar bei einem Eindringen von Produktionsschlacken in die Legierung bis zu einem Anteil von 1,0 %, wobei diese Schlacken aus Oxiden und Sulfiden von Metallen entstehen, und bis zu einem Anteil von 1,0 % der inaktiven Metalle erreicht, die als Begleitstoffe in der Schicht auftreten.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.

Die obere und die untere Grenze des Gehalts an Legierungskomponenten sind entsprechend der gestellten Aufgabe und den wirtschaftlichen Gründen gewählt. Die untere Grenze des Siliziumgehalts in der Legierung ist dadurch bedingt, dass bei einem Gehalt von weniger als 45 % die modifizierenden Eigenschaften dieses Elements kaum erkennbar sind. Außerdem ist Silizium ein Lösungsmittel für die andere Legierungskomponente. Eine Erhöhung des Siliziumanteils bis mehr als 78 % ist nicht zweckmäßig, denn das führt nicht zu einer weiteren Erhöhung der modifizierenden Fähigkeit dieses Elements, sondern zum Wertanstieg der Legierung.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. In addition, 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.

Die Seltenerdmetalle werden in die Legierung für die Stabilisierung der Ergebnisse der sphäroidisierenden Modifikation wegen der Neutralisation der Beimischung der Buntmetall-Deglobulasatoren (Pb, Sn, Sb und andere) durch deren Kopplung mit der feindispersen Verbindung eingeführt, die auch zusätzliche Graphitisierungszentren sind. Sulfide und Oxysulfide der Seltenerdmetalle mit hoher Dichte, die mit der Dichte des Flüssigeisens zu vergleichen ist, dienen auch als Kristallisationszentren von Graphit und stärken dabei die graphitisierenden Wirkung. Bei einem Gehalt von weniger als 0,1 % in der Legierung ist ihre Wirkung auf die Gusseiseneigenschaften wenig bemerkbar. Ein Gehalt an Seltenerdmetallen von höher als 2,2 % ist wegen der Abschwächung der Steigerung der graphitisierenden Fähigkeit dieser Metalle und der Verteuerung der Legierung unzweckmäßig. Unter den individuellen Seltenerdmetallen sind Lantan und Neodym zu nennen.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. Among the individual rare earth metals are lanthanum and neodymium.

Die Einführung von Strontium in die Legierung führt zu einer Verbesserung der Graphitform und zu einer plötzlichen Steigerung der graphitisierenden Fähigkeit des Strontiums. Aber das graphitisierende Potential des Strontiums nimmt beim Vorhandensein von Kalzium und Aluminium bedeutend ab. Die untere Grenze des Stronziumgehalts in der Legierung ist dadurch bedingt, dass bei einem Anteil von mindestens 0,1 % Sr in dieser Legierung der Zusatz dieser Legierung im Gusseisen wenig wirksam ist. Die obere Grenze des Strontiumgehalts in der Legierung ist durch die Möglichkeiten des Arbeitsvorgangs zur Gewinnung der Legierung begrenzt.The introduction of 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.

Das Vorhandensein von Kalzium und Magnesium in der Legierung fördert die Verbesserung der Entstehungsbedingungen für die Graphitkeime bei der Kristallisierung des Gusseisens, und je größer der Kalziumanteil ist, desto mehr Magnesium soll die Legierung enthalten. Bei einem Anteil an Kalzium von 0,1 % soll die Legierung höchstens 0,15 % Magnesium enthalten. Die Obergrenze des Gehalts an Kalzium (1,5 %) entspricht auch der Obergrenze des Magnesiumsgehalts (7,0 %) in der Legierung. Ein Kalziumgehalt von mehr als 1,5 % in der Legierung fördert eine Senkung der Auflösungsgeschwindigkeit im Flüssiggusseisen infolge der Sperre der Angriffsfläche mit den entstehenden Silikaten.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.

Der Aluminiumanteil soll höchstens 2,0 % sein, denn Aluminium senkt die graphitisierende Fähigkeit von Strontium. Die Untergrenze von Aluminium in der Legierung erklärt sich durch einen großen Verbrauch, der mit dem Raffinieren des Ferrosiliziums aus Aluminium verbunden ist, weil die Industriesorten von Ferrosilizium 2,5 % Aluminium enthalten.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.

Das Vorhandensein von Magnesium in der Legierung in einer Menge von weniger als 0,1 % stört die Stabilisierung der Bestandteile der Legierung und garantiert nicht den notwendigen Gehalt an Strontium, Kalzium und Aluminium in engen Grenzen. Das Magnesium erhöht die Strontiumlöslichkeit in der eisenkieselartigen Schmelze und ermöglicht, den Gehalt an diesem Element an der Obergrenze (2,0 %) stabil zu halten, sogar bei einem minimalen Gehalt an Silizium. Außerdem ist Magnesium ein wichtiges, sphäroidisierendes Element. Ein Anteil an Magnesium von mehr als 7 % in der Legierung führt zu einem erhöhten Abbrand der Legierung und zu einem Pyroeffekt bei der Einführung des Modifikators in das Flüssiggusseisen. Darum ist dieser Gehalt an Magnesium in der Legierung wirtschaftlich und ökologisch nicht zweckmäßig.The presence of 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. In addition, 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.

Das Zirkonium ist in die Legierung für die Nivellierung der schädlichen Wirkung des Aluminiums auf den graphitisierenden Einfluss des Strontiums eingeführt. Dabei entspricht die Untergrenze des Zirkoniumgehalts der unteren Grenze des Gehalts an Aluminium in der Legierung, und die Obergrenze des Zirkoniumgehalts entspricht der größten Menge des Aluminiums in der Legierung. Es ist bekannt, dass Strontium beim Vorhandensein von Aluminium in den eisenkieselartigen Modifikatoren seine graphitisierende Eigenschaften nicht stabil zeigt und die Verwendung von solchen Modifikatoren nicht immer zur absoluten Beseitigung des Aufhellens in den Eisenstücken führt. Das in die Legierung in der angegebenen Menge eingeführte Zirkonium stabilisiert die leistungsstarke, graphitisierende Fähigkeit von Strontium infolge der Entstehung der festen Verbindungen ZrAl2, ZrAl3 und anderen und gibt die Möglichkeit, das Aufhellen in dünnwandigem Guss zu beseitigen. Ein Zirkoniumgehalt von weniger als 0,1 % in der Legierung garantiert nicht eine stabile Wirkung des Strontiums, wenn die Legierung 0,3 % Aluminium enthält. Wenn es in der Legierung 2,0 % Zirkonium gibt, kann die schädliche Wirkung des Aluminiums, sogar wenn dessen Anteil 2,0 % beträgt, vermieden werden.Zirconium is entered into alloy for leveling harmful effects of aluminum on the graphitizing influence of strontium. Here, the lower limit of the zirconium content corresponds to the lower limit of the content of aluminum in the alloy, and the upper limit of the zirconium content corresponds to the largest amount of the aluminum in the alloy. It is known that strontium, in the presence of aluminum in the iron-pebble type modifiers, does not display its graphitizing properties stably and the use of such modifiers does not always result in the absolute elimination of brightening in the iron pieces. 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.

Beispiel 1example 1

Gewinnung der Legierung für die Gusseisenmodifikation.
Die Legierung (Tabelle 1) wird in einem Induktionsofen IST 1,0) bei der Legierung von Silizium, Stahlschrott, Mischmetall oder Lautanoxid, Magnesium, Silicozirkonium und Stronziumkarbonat hergestellt. Die Schmelze wird in Blockform gegossen. Nach der Abkühlung wird die Legierung von der Schlacke getrennt und mit einem Backenquetscher (DLSC 80) aufgebrochen, wobei die Bruchteile einen Durchmesser von 1-5 mm aufweisen.Extraction of the alloy for the cast iron modification.
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.

Beispiel 2Example 2

Vergleich der Wirkung der Legierung für die Modifizierung.
Für den Vergleich der Wirkung der Legierung wird Gusseisen verwendet, der in einem Induktionsofen (IST 0,1) geschmolzen wird. Die Gusseisenmodifikation mittels der Legierung wird in einer Gießpfanne durchgeführt. Es wurden Legierungen von bekanntem Gehalt und von dem Gehalt gemäß der Erfindung miteinander verglichen. In der Tabelle 1 sind die ersten drei bekannte Legierungsgehalte und die letzten vier Legierungsgehalte gemäß der Erfindung.Comparison of the effect of the alloy for the modification.
To compare the effect of the alloy, use is made of cast iron, which is melted in an induction furnace (ACT 0,1). The cast iron modification by means of the alloy is carried out in a ladle. Alloys of known content and content according to the invention were compared. In Table 1, the first three known alloy contents and the last four alloy contents are according to the invention.

In der Tabelle 2 sind Ergebnisse der Gusseisenmodifizierung mittels der Legierungen der Gehalte 1-7 dargestellt. Mechanische Tests wurden mit Mustern von 10 mm nach dem GOST 1497-84 und die Größe des Aufhellens im Guss wurde mit einer Wandstärke von 3 mm gemessen. Tabelle 1 Elemente Massenanteil der Elemente Bekannter Gehalt Gehalt gemäß der Erfindung 1 2 3 4 5 6 7* Silizium 15 50 90 78 45 77 50 Seltenerdmetalle - - - 0,1 0,3 (La) 2,2 1,5 Strontium 0,1 5 0,1 0,8 0,1 0,8 2,0 Kalzium 0,05 0,05 0,1 0,15 0,4 0,15 1,5 Aluminium 0,5 0,5 0,5 0,3 0,8 0,5 2,0 Zirkonium 10 5 0,3 1,2 0,1 0,1 2,0 Magnesium - - - 0,1 5,5 0,3 7,0 Eisen fehlt fehlt fehlt fehlt fehlt fehlt fehlt * Die Legierung enthält Produktionsschlacke und Fremdstoffe, 1% von jedem Element. Tabelle 2 Legierung σB, MPa δ, % Tiefe des Aufhellens, mm 1 150 ≤0,2 1,4 2 190 ≤0,2 fehlt 3 210 ≤0,2 fehlt 4 250 0,5 fehlt 5 620 2,2 fehlt 6 330 1,2 fehlt 7 530 3,5 fehlt In Table 2, results of the cast iron modification by means of alloys of contents 1-7 are shown. Mechanical tests were carried out with samples of 10 mm according to the GOST 1497-84 and the size of the brightening in the casting was measured with a wall thickness of 3 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. alloy σ B , MPa δ,% Depth of lightening, mm 1 150 ≤0,2 1.4 2 190 ≤0,2 is missing 3 210 ≤0,2 is missing 4 250 0.5 is missing 5 620 2.2 is missing 6 330 1.2 is missing 7 530 3.5 is missing

Aus der Tabelle 2 folgt, dass die Legierung eine stabile Liquidierung von Bleiche in dünnwandigem Gussstück bei erhöhter Haltbarkeit und Plastizität des Gusseisens ermöglicht.It follows from Table 2 that the alloy enables stable bleaching of bleach in thin-walled casting with increased durability and plasticity of the cast iron.

Claims (5)

  1. Alloy for modifying cast iron, the said alloy including silicon, calcium, aluminium, zirconium and iron, characterised in that the said alloy also includes magnesium and rare earth metals with components at the following ratios (the mass is given as a %): Silicon 45-78 Rare earth metals 0,1-2,2 Strontium 0,1-2,0 Calcium 0,1-1,5 Aluminium 0,3-2,0 Magnesium 0,1-7,0 Zirconium 0,1-2,0 Iron remainder
  2. Alloy according to claim 1, characterised in that the said alloy includes 0,1 - 1,0 % magnesium, 0,1 - 0,2 % calcium, 0,3 - 0,5 % aluminium and 0,1 - 0,3 % rare earth metals.
  3. Alloy according to claim 1, characterised in that the said alloy includes 4,0 - 7,0 % magnesium, 0,2- 1,0 % calcium, 0,5- 1,5 % aluminium, 0,1 - 0,3 % zirconium, and in that individual elements are used as rare earth metals.
  4. Alloy according to claim 3, characterised in that lanthanum and/or neodymium are used as individual rare earth metals in a proportion of 0,2 - 0,5 % of the total amount.
  5. Alloy according to claim 1, characterised in that the said alloy includes slag and impurities up to 1 % of each substance.
EP04808959A 2004-11-04 2004-11-04 Alloy for modifying iron Not-in-force EP1811051B1 (en)

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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 (en) * 1978-01-10 1980-06-05 Институт Проблем Литья Ан Украинской Сср Modifier
JPS5616613A (en) * 1979-07-21 1981-02-17 Toyota Motor Corp Additive for cast iron
DE3824175A1 (en) * 1988-07-16 1990-01-18 Metallgesellschaft Ag METHOD FOR PRODUCING CAST IRON WITH SPHERICAL GRAPHITE AND / OR VERMICULAR GRAPHITE
SU1723172A1 (en) * 1990-05-17 1992-03-30 Липецкий Филиал Всесоюзного Проектно-Технологического Института Литейного Производства Modifier for cast iron
DE4124159C2 (en) * 1991-07-20 1996-08-14 Sueddeutsche Kalkstickstoff Master alloy for the treatment of cast iron melts
GB9600807D0 (en) * 1996-01-16 1996-03-20 Foseco Int Composition for inoculating low sulphur grey iron
NO306169B1 (en) * 1997-12-08 1999-09-27 Elkem Materials Cast iron grafting agent and method of making grafting agent
US6793707B2 (en) * 2002-01-10 2004-09-21 Pechiney Electrometallurgie Inoculation filter

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ATE415499T1 (en) 2008-12-15
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DE502004008559D1 (en) 2009-01-08
WO2006049525A1 (en) 2006-05-11
EA008521B1 (en) 2007-06-29
EA200501649A1 (en) 2006-06-30

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