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EP1283913A1 - Method for producing spheroidal graphite cast iron - Google Patents

Method for producing spheroidal graphite cast iron

Info

Publication number
EP1283913A1
EP1283913A1 EP01927562A EP01927562A EP1283913A1 EP 1283913 A1 EP1283913 A1 EP 1283913A1 EP 01927562 A EP01927562 A EP 01927562A EP 01927562 A EP01927562 A EP 01927562A EP 1283913 A1 EP1283913 A1 EP 1283913A1
Authority
EP
European Patent Office
Prior art keywords
cast iron
spheroidal graphite
graphite cast
pretreatment
magnesium
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
EP01927562A
Other languages
German (de)
French (fr)
Other versions
EP1283913B1 (en
Inventor
Karl Keller
Roland Siclari
Thomas Margaria
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.)
Ferroglobe France SAS
Original Assignee
Georg Fischer Disa AG
Pechiney Electrometallurgie SAS
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Application filed by Georg Fischer Disa AG, Pechiney Electrometallurgie SAS filed Critical Georg Fischer Disa AG
Publication of EP1283913A1 publication Critical patent/EP1283913A1/en
Application granted granted Critical
Publication of EP1283913B1 publication Critical patent/EP1283913B1/en
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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

Definitions

  • the invention relates to a process for producing spheroidal graphite cast iron comprising at least the process steps pretreatment with pure magnesium in a converter and inoculant addition when pouring into the mold.
  • a method and a device for producing spheroidal graphite cast iron are known from US Pat. No. 5,098,651.
  • a treatment vessel for the cast iron melt pure magnesium is introduced into a vessel compartment which is accessible from the outside and which is in contact via openings in the partition between the vessel compartment and the rest of the treatment vessel.
  • the converter is moved from a horizontal position taken to introduce the magnesium to a vertical position, the magnesium is wetted by the melt and produces
  • the reaction with the pure magnesium does the following: Mineral compounds consisting of oxides, sulfates, silicates and other compounds with magnesium are formed from the non-metallic components of the melt.
  • the melt is set in motion by the vapor pressure of the magnesium.
  • the mineral compounds coagulate, agglomerate and float on the surface of the bath due to their lower specific weight.
  • the slags formed in this way can be removed by skimming.
  • This method is characterized inter alia by a bath composition with a high purity of, for example, less than 10 ppm of dissolved oxygen and a low nucleating agent concentration of, for example, less than 100 ppm of non-metallic particles.
  • WO 99/45156 A1 specifies a method in which, prior to the actual treatment with magnesium, the cast iron melt is used in successive steps with calcium carbide to remove oxygen and Sulfur, is treated with mill scale to supply oxygen and with aluminum oxide or with calcium oxide to form calcium aluminates or calcium aluminum silicates. This ensures that after the subsequent treatment with magnesium, the cast iron has non-metallic inclusions that are plastic during machining and thus serve as a lubricant. In the subsequent process steps, excessive amounts of vaccine are often added. When pouring into the mold, there is a risk that the quality will be adversely affected because the reaction products lead to uncontrollable errors, such as slags, oxides and undissolved vaccine particles. Uncontrollable conditions arise with regard to the nucleation state. Because the state of nucleation is not exactly known, the dosage of the vaccine cannot be determined exactly. In the ignorance of the nucleation state, it is often overdosed. This is expensive and not beneficial for the quality of the cast iron.
  • This object is achieved by a process for producing spheroidal graphite cast iron comprising at least the process steps pretreatment with pure magnesium in a converter and addition of inoculant when pouring into the mold, the solubility of the substances formed in the pretreatment and inoculation being adjustable.
  • the total amount of substances added is kept as low as possible for the production of spheroidal graphite cast iron. This is achieved in that the amount of an FeSi or CaSi-based inoculant which is added to the mold when poured is substantially smaller, preferably four times smaller, than the amount of the compound or mixture forming oxysulfides used in the pretreatment with magnesium.
  • the method proposed here is based on the known pretreatment with pure metallic magnesium in a closed converter.
  • the process leads to an improvement in the quality of the spheroidal graphite cast iron which is used in the
  • Magnesium converter is manufactured because casting errors due to oxides and slags and other errors caused by vaccines are avoided. In existing foundries with the magnesium converter, the process can be used easily and without the need for additional process steps. By adding the oxysulfide-forming compound or mixture with the pure metallic magnesium in the pretreatment, both cleaning of the melt and preconditioning of the nucleation state are achieved in a single process step.
  • the chemical oxygen and sulfur activity in the melt can be set as precisely as possible, while as little foreign matter as possible has to be added per unit weight of cast iron.
  • the nuclei which are formed after the addition of the oxysulfide-forming compound or mixture by the reaction with the melt, have a sufficiently long life in the melt.
  • the formation of an oxysulfide in the pretreatment has shown that this has the least adverse effect on the final purity of the cast iron alloy and at the same time has a positive effect on the solubility of the nucleating substances.
  • the melt is preconditioned, i.e. optimally prepared for solidification in the mold.
  • This optimal preparation largely reduces the need for inoculants when pouring.
  • the amount and the type of compound or mixture introduced in the pretreatment in the magnesium converter can be selected such that it is even possible to dispense with the process step of adding inoculants during pouring in the mold.
  • the purity of the cast iron melt is influenced as little as possible by the small addition of foreign substances.
  • the use of oxysulfides has the following advantages: The specific weight differs only slightly from the specific weight of the melt, so that a homogeneous
  • the grain size and the grain shape can be selected in such a way that the germs are retained over a longer period.
  • elements from the groups Ila and lilac of the periodic table for example Mg, Ca, Ba, La or rare earths, are advantageously chosen.
  • inoculant In the subsequent pouring out of the casting furnace into the mold, only a small addition of inoculant is necessary to finally set the nucleation state. Because the oxysulfides that were formed in the pretreatment have a higher nucleation capacity than the previously known inoculants, a small amount, ie at most a quarter, is sufficient the amount added in the pretreatment to control nucleation in the mold. With the inoculant, which is added when pouring into the mold, the speed, the crystal shape and the crystal distribution during solidification can be controlled and finally adjusted. For example, an alloy based on FeSi or CaSi or a compound with Ca, Ba, Mg, Au, Ge, La or rare earths is used as the inoculant during casting.
  • Pretreatment with oxysulfide-forming compounds or mixtures combined with magnesium treatment in the converter, on the one hand, and the reduced addition of inoculant during pouring, on the other hand, has the following further advantages: Because fewer foreign bodies are introduced, considerably less slag is formed than in the conventional process, which means that less iron is lost with the slag lost. Because fewer inoculants are added to the cast iron melt, fewer foreign bodies are trapped between the crystals during solidification. This reduces the tendency towards casting errors. Fewer inclusions of magnesium, silicon or oxygen compounds have a favorable influence on the microporosity of the cast iron and promote a uniform solidification in the form.
  • a lower microporosity is also advantageous for the interaction of the melt with the molding material mixture or with the sand from which the mold is formed. This makes the surface of the cast iron product cleaner and more uniform, i.e. H. there are fewer surface defects. This makes it easier to machine the surface of the cast iron product.
  • FIGS. 1 and 2 show a microscope image of a spheroidal graphite particle with an undissolved core of a vaccine therein.
  • Figure 2 shows an enlargement from the central area of the particle of Figure 1.
  • the spheroidal graphite particle was obtained from a melt which was inoculated with a compound of iron, silicon and lanthanum.
  • the analysis of the core of the spheroidal graphite particle showed the following composition: 41.7% La, 47.2% S, 9.1% Mg and 1.7% Si. This shows that the poor solubility of the compounds or mixtures which form small amounts and which form oxysulfides has a favorable influence on the formation of spheroidal graphite particles and on the casting properties.
  • the spheroidal graphite cast iron products that are manufactured by this process are characterized by a high degree of purity at relatively low manufacturing costs. Less slag has to be disposed of or recycled and the dosage of the inoculants can be made significantly smaller.
  • the effort for measuring and controlling the casting process, in particular the equipment for analyzing the melt, can be considerably reduced because the process is more stable and more reproducible.
  • the quantity ratio of the foreign bodies added can be adjusted between pretreatment and vaccine.
  • the mutual adaptation between pretreatment and the addition of inoculant allows both the nucleation in the melt and the solidification in the mold to be coordinated. With the right choice of the type and the amount of foreign bodies, it may be possible to dispense with an addition when pouring into the mold.
  • Spheroidal graphite cast iron (GJS) is characterized by mechanical properties that come very close to the mechanical properties of cast steel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (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)
  • Mold Materials And Core Materials (AREA)
  • Pivots And Pivotal Connections (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Dental Preparations (AREA)
  • Glass Compositions (AREA)

Abstract

A method for producing high-purity spheroidal graphite cast iron. The method comprises at least the steps of pretreating the melt in a closed converter and adding an inocculant when casting it into the mold. The solubility of the substances formed during the pretreatment and during the addition of the inocculant an be adjusted. The nucleation in the melt and the solidification in the mold can be brought into conformity by coordinating the pretreatment and the addition of inocculant.

Description

Verfahren zur Herstellung von Kugelgraphit-GusseisenProcess for the production of spheroidal graphite cast iron
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Kugelgraphit- Gusseisen umfassend zumindest die Verfahrensschritte Vorbehandlung mit reinem Magnesium in einem Konverter und Impfmittelzugabe beim Abgiessen in die Form.The invention relates to a process for producing spheroidal graphite cast iron comprising at least the process steps pretreatment with pure magnesium in a converter and inoculant addition when pouring into the mold.
Aus der US 5098651 sind ein Verfahren und eine Vorrichtung zur Herstellung von Kugelgraphit-Gusseisen bekannt. In einem Konverter, ein Behandlungsgefäss für die Gusseisenschmelze, wird in einem Gefässabteil, das von aussen zugänglich ist und das über Öffnungen in der Trennwand zwischen dem Gefässabteil und dem restlichen Behandlungsgefäss in Kontakt steht, reines Magnesium eingebracht. Wenn der Konverter von einer horizontalen Lage, die eingenommen wurde um das Magnesium einzubringen, in einer vertikalen Lage gebracht wird, wird das Magnesium von der Schmelze benetzt und unter Erzeugung vonA method and a device for producing spheroidal graphite cast iron are known from US Pat. No. 5,098,651. In a converter, a treatment vessel for the cast iron melt, pure magnesium is introduced into a vessel compartment which is accessible from the outside and which is in contact via openings in the partition between the vessel compartment and the rest of the treatment vessel. When the converter is moved from a horizontal position taken to introduce the magnesium to a vertical position, the magnesium is wetted by the melt and produces
Reaktionswärme aufgelöst. Die Reaktion mit dem reinen Magnesium bewirkt folgendes: Aus den nicht-metallischen Bestandteilen der Schmelze entstehen mineralische Verbindungen, bestehend aus Oxiden, Sulfaten, Silikaten und anderen Verbindungen mit Magnesium. Durch den Dampfdruck des Magnesiums wird die Schmelze in eine intensive Bewegung versetzt. Die mineralischen Verbindungen koagulieren, agglomerieren und schwimmen, aufgrund des niedrigeren spezifischen Gewichtes, an der Badoberfläche auf. Von der Badoberfläche können die so gebildeten Schlacken durch Abschöpfen entfernt werden. Dieses Verfahren zeichnet sich unter anderem aus durch eine Badzusammensetzung mit einer hohen Reinheit von beispielsweise weniger als 10 ppm gelöstem Sauerstoff und einer niedrigen Keimbildnerkonzentration von beispielsweise weniger als 100 ppm nicht-metallischen Partikeln.Heat of reaction dissolved. The reaction with the pure magnesium does the following: Mineral compounds consisting of oxides, sulfates, silicates and other compounds with magnesium are formed from the non-metallic components of the melt. The melt is set in motion by the vapor pressure of the magnesium. The mineral compounds coagulate, agglomerate and float on the surface of the bath due to their lower specific weight. The slags formed in this way can be removed by skimming. This method is characterized inter alia by a bath composition with a high purity of, for example, less than 10 ppm of dissolved oxygen and a low nucleating agent concentration of, for example, less than 100 ppm of non-metallic particles.
In der WO 99/45156 A1 wird ein Verfahren angegeben, in dem vor der eigentlichen Behandlung mit Magnesium die Gusseisenschmelze in auf einander folgenden Schritten mit Calciumcarbid zum Entfernen von Sauerstoff und Schwefel, mit Walzzunder zum Zuführen von Sauerstoff und mit Aluminiumoxid oder mit Calciumoxid zum Bilden von Calciumaluminaten oder Calciumaluminium- silikaten behandelt wird. Hierdurch wird erreicht, dass nach der nachfolgenden Behandlung mit Magnesium das Gusseisen nicht-metallische Einschlüsse aufweist, die bei der spanabhebenden Bearbeitung plastisch sind und somit als Schmiermittel dienen. In den nachfolgenden Verfahrensschritten werden oft zu grosse Mengen an Impfmittel zugegeben. Beim Abgiessen in die Form besteht dann die Gefahr, dass die Qualität nachteilig beeinträchtigt wird, weil die Reaktionsprodukte zu unkontrollierbare Fehler, wie Schlacken, Oxide und nicht aufgelöste Impfmittelpartikel führen. Es entstehen unkontrollierbare Verhältnisse in bezug auf den Keimbildungszustand. Weil der Keimbildungszustand nicht genau bekannt ist, kann die Dosierung der Impfmittel nicht genau bestimmt werden. Im Unwissen des Keimbildungszustandes wird häufig überdosiert. Dies ist teuer und für die Qualität des Gusseisens nicht vorteilhaft.WO 99/45156 A1 specifies a method in which, prior to the actual treatment with magnesium, the cast iron melt is used in successive steps with calcium carbide to remove oxygen and Sulfur, is treated with mill scale to supply oxygen and with aluminum oxide or with calcium oxide to form calcium aluminates or calcium aluminum silicates. This ensures that after the subsequent treatment with magnesium, the cast iron has non-metallic inclusions that are plastic during machining and thus serve as a lubricant. In the subsequent process steps, excessive amounts of vaccine are often added. When pouring into the mold, there is a risk that the quality will be adversely affected because the reaction products lead to uncontrollable errors, such as slags, oxides and undissolved vaccine particles. Uncontrollable conditions arise with regard to the nucleation state. Because the state of nucleation is not exactly known, the dosage of the vaccine cannot be determined exactly. In the ignorance of the nucleation state, it is often overdosed. This is expensive and not beneficial for the quality of the cast iron.
Ausgehend von diesem Stand der Technik ist es Aufgabe der Erfindung, ein Verfahren zur Herstellung von Kugelgraphit-Gusseisen anzugeben, das zumindest die Verfahrensschritte Vorbehandlung mit reinem Magnesium in einem Konverter und Impfmittelzugabe beim Abgiessen in die Form umfasst, wobei möglichst wenig unnötige Oxide, Schlacken oder Impfmittelreste in die Schmelze und in das Gussstück eingebracht werden.Starting from this prior art, it is an object of the invention to provide a process for the production of spheroidal graphite cast iron which comprises at least the process steps pretreatment with pure magnesium in a converter and addition of inoculant when pouring into the mold, with as little unnecessary oxides, slags or Remnants of inoculant are introduced into the melt and into the casting.
Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung von Kugelgraphit- Gusseisen umfassend zumindest die Verfahrensschritte Vorbehandlung mit reinem Magnesium in einem Konverter und Impfmittelzugabe beim Abgiessen in die Form, wobei die Löslichkeit der in der Vorbehandlung und in der Impfung gebildeten Substanzen einstellbar ist.This object is achieved by a process for producing spheroidal graphite cast iron comprising at least the process steps pretreatment with pure magnesium in a converter and addition of inoculant when pouring into the mold, the solubility of the substances formed in the pretreatment and inoculation being adjustable.
Bevorzugte Weiterbildungen der Erfindung ergeben sich aus den abhängigen Ansprüchen. Es ist von Vorteil, dass zur Herstellung von Kugelgraphit-Gusseisen möglichst keine Verunreinigungen im Gusseisen eingebracht werden. Dies wird dadurch erreicht, dass die Vorbehandlung mit einer Mischung oder einer Verbindung von reinem metallischen Magnesium mit einem oder mehreren Metallen aus den Gruppen lla und lila des Periodensystems und mit Schwefel durchgeführt wird. Dies wird auch dadurch erreicht, dass die Vorbehandlung mit einer Mischung oder einer Verbindung von reinem metallischen Magnesium mit Schwefel und mit Ba, Ca, La oder seltenen Erden, wobei die Mischung oder Verbindung in der Metallschmelze Oxysulfiden bildet, durchgeführt wird.Preferred developments of the invention result from the dependent claims. It is advantageous that for the production of spheroidal graphite cast iron, as little contamination as possible is introduced into the cast iron. This is achieved in that the pretreatment is carried out with a mixture or a compound of pure metallic magnesium with one or more metals from groups Ila and lilac in the periodic table and with sulfur. This is also achieved in that the pretreatment is carried out with a mixture or a compound of pure metallic magnesium with sulfur and with Ba, Ca, La or rare earths, the mixture or compound forming oxysulfides in the molten metal.
Es ist auch von Vorteil, dass zur Herstellung von Kugelgraphit-Gusseisen die Gesamtmenge der zugegebenen Substanzen möglichst gering gehalten wird. Dies wird dadurch erreicht, dass die Menge eines auf FeSi oder CaSi basierenden Impfmittels, das beim Abgiessen in die Form zugegeben wird, wesentlich kleiner, vorzugsweise viermal kleiner ist, als die in der Vorbehandlung mit Magnesium eingesetzten Menge der Oxysulfiden bildenden Verbindung oder Mischung.It is also advantageous that the total amount of substances added is kept as low as possible for the production of spheroidal graphite cast iron. This is achieved in that the amount of an FeSi or CaSi-based inoculant which is added to the mold when poured is substantially smaller, preferably four times smaller, than the amount of the compound or mixture forming oxysulfides used in the pretreatment with magnesium.
Das hier vorgeschlagene Verfahren geht aus von der bekannten Vorbehandlung mit reinem metallischen Magnesium im geschlossenen Konverter. Das Verfahren führt zu einer Verbesserung der Qualität des Kugelgraphit-Gusseisens, das imThe method proposed here is based on the known pretreatment with pure metallic magnesium in a closed converter. The process leads to an improvement in the quality of the spheroidal graphite cast iron which is used in the
Magnesiumkonverter hergestellt wird, weil Gussfehler durch Oxide und Schlacken und weitere durch Impfmittel bedingten Fehler vermieden werden. In bestehenden Giessereien mit dem Magnesiumkonverter kann das Verfahren einfach und ohne Einschaltung zusätzlicher Verfahrensschritten angewendet werden. Durch die Zugabe der Oxysulfiden bildenden Verbindung oder Mischung mit dem reinen metallischen Magnesium wird in der Vorbehandlung sowohl eine Reinigung der Schmelze als auch eine Vorkonditionierung des Keimbildungszustandes in einem einzelnen Verfahrensschritt erreicht. Die chemische Sauerstoff- und Schwefelaktivität in der Schmelze wird möglichst genau einstellbar, während möglichst wenig Fremdkörper pro Gewichtseinheit Gusseisen zugegeben werden muss. Weil die gebildeten Oxysulfide eine relativ schlechte Löslichkeit in der Gusseisenschmelze aufweisen, haben die Keime, die nach der Zugabe der Oxysulfiden bildenden Verbindung oder Mischung durch die Reaktion mit der Schmelze gebildet werden, in der Schmelze eine ausreichend lange Lebensdauer. Es kann von einer hohen Keimbildungskapazität der Oxysulfiden gesprochen werden. Die Bildung eines Oxysulfides in der Vorbehandlung hat gezeigt, dass hierdurch die endgültige Reinheit der Gusseisenlegierung am wenigsten nachteilig beeinträchtigt wird und gleichzeitig die Löslichkeit der keimbildenden Substanzen positiv beeinflusst wird.Magnesium converter is manufactured because casting errors due to oxides and slags and other errors caused by vaccines are avoided. In existing foundries with the magnesium converter, the process can be used easily and without the need for additional process steps. By adding the oxysulfide-forming compound or mixture with the pure metallic magnesium in the pretreatment, both cleaning of the melt and preconditioning of the nucleation state are achieved in a single process step. The chemical oxygen and sulfur activity in the melt can be set as precisely as possible, while as little foreign matter as possible has to be added per unit weight of cast iron. Because the oxysulfides formed have a relatively poor solubility in the Cast iron melt, the nuclei, which are formed after the addition of the oxysulfide-forming compound or mixture by the reaction with the melt, have a sufficiently long life in the melt. One can speak of a high nucleation capacity of the oxysulfides. The formation of an oxysulfide in the pretreatment has shown that this has the least adverse effect on the final purity of the cast iron alloy and at the same time has a positive effect on the solubility of the nucleating substances.
Durch die Zugabe der Oxysulfiden bildenden Verbindung oder Mischung in derBy adding the oxysulfide-forming compound or mixture in the
Vorbehandlung wird die Schmelze vorkonditioniert, d.h. optimal vorbereitet auf die Erstarrung in der Form. Durch diese optimale Vorbereitung wird der Bedarf an Impfmittel beim Abgiessen weitgehend reduziert. Die Menge und die Art der bei der Vorbehandlung im Magnesiumkonverter eingebrachte Verbindung oder Mischung kann derart gewählt werden, dass sogar auf den Verfahrensschritt der Zugabe von Impfmitteln beim Abgiessen in der Form verzichtet werden kann. Durch die geringe Zugabe von Fremdsubstanzen wird die Reinheit der Gusseisenschmelze möglichst wenig negativ beeinflusst. Die Verwendung von Oxysulfiden hat weiterhin folgende Vorteile: Das spezifische Gewicht weicht nur wenig ab vom spezifischen Gewicht der Schmelze, so dass eine homogenePretreatment, the melt is preconditioned, i.e. optimally prepared for solidification in the mold. This optimal preparation largely reduces the need for inoculants when pouring. The amount and the type of compound or mixture introduced in the pretreatment in the magnesium converter can be selected such that it is even possible to dispense with the process step of adding inoculants during pouring in the mold. The purity of the cast iron melt is influenced as little as possible by the small addition of foreign substances. The use of oxysulfides has the following advantages: The specific weight differs only slightly from the specific weight of the melt, so that a homogeneous
Durchmischung einfach erreicht werden kann. Die Komgrösse und die Kornform sind derart wählbar, dass die Keime über eine längere Zeit erhalten bleiben. Als Zugabe zum Magnesium in der Vorbehandlung werden vorteilhaft Elemente aus den Gruppen lla und lila des Periodensystems, beispielsweise Mg, Ca, Ba, La oder seltene Erden gewählt.Mixing can be easily achieved. The grain size and the grain shape can be selected in such a way that the germs are retained over a longer period. As an addition to the magnesium in the pretreatment, elements from the groups Ila and lilac of the periodic table, for example Mg, Ca, Ba, La or rare earths, are advantageously chosen.
Beim nachfolgenden Abgiessen aus dem Giessofen in die Form ist lediglich eine geringe Zugabe von Impfmittel zur endgültigen Einstellung des Keimbildungszustandes erforderlich. Weil die Oxysulfide, die in der Vorbehandlung gebildet wurden, eine höhere Keimbildungskapazität als die bisher bekannten Impfmittel haben, reicht eine kleine Menge, d.h. höchstens ein Viertel der Menge, die in der Vorbehandlung zugegeben wurde, aus um die Keimbildung in der Form zu steuern. Mit dem Impfmittel, das beim Abgiessen in die Form zugegeben wird, kann die Geschwindigkeit, die Kristallform und die Kristallverteilung bei der Erstarrung gesteuert und endgültig eingestellt werden. Als Impfmittel beim Abgiessen wird beispielsweise eine auf FeSi oder CaSi basierende Legierung oder Verbindung mit Ca, Ba, Mg, Au, Ge, La oder seltenen Erden eingesetzt.In the subsequent pouring out of the casting furnace into the mold, only a small addition of inoculant is necessary to finally set the nucleation state. Because the oxysulfides that were formed in the pretreatment have a higher nucleation capacity than the previously known inoculants, a small amount, ie at most a quarter, is sufficient the amount added in the pretreatment to control nucleation in the mold. With the inoculant, which is added when pouring into the mold, the speed, the crystal shape and the crystal distribution during solidification can be controlled and finally adjusted. For example, an alloy based on FeSi or CaSi or a compound with Ca, Ba, Mg, Au, Ge, La or rare earths is used as the inoculant during casting.
Die Vorbehandlung mit Oxysulfiden bildenden Verbindungen oder Mischungen kombiniert mit der Magnesiumbehandlung im Konverter einerseits und die reduzierte Impfmittelzugabe beim Abgiessen andererseits hat folgende weiteren Vorteile: Weil wenige Fremdkörper eingebracht werden, werden erheblich weniger Schlacken gebildet als beim herkömmlichen Verfahren, dadurch geht mit der Schlacke weniger Eisen verloren. Weil an die Gusseisenschmelze insgesamt weniger Impfmittel zugeführt wird, werden bei der Erstarrung weniger Fremdkörper zwischen den Kristallen eingeschlossen. Hierdurch wird die Neigung zu Gussfehler reduziert. Weniger Einschlüsse von Magnesium-, Silicium- oder Sauerstoffverbindungen haben einen günstigen Einfluss auf die Mikroporosität des Gusseisens und fördern eine gleichmässige Erstarrung in der Form. Eine niedrigere Mikroporosität ist auch vorteilhaft für die Wechselwirkung der Schmelze mit der Formstoffmischung oder mit dem Sand, aus dem die Form ausgebildet ist. Hierdurch wird die Oberfläche des Gusseisenproduktes sauberer und gleichmässiger, d. h. es treten weniger Oberflächenfehler auf. Dadurch wird die Bearbeitbarkeit der Oberfläche des Gusseisenproduktes leichter.Pretreatment with oxysulfide-forming compounds or mixtures combined with magnesium treatment in the converter, on the one hand, and the reduced addition of inoculant during pouring, on the other hand, has the following further advantages: Because fewer foreign bodies are introduced, considerably less slag is formed than in the conventional process, which means that less iron is lost with the slag lost. Because fewer inoculants are added to the cast iron melt, fewer foreign bodies are trapped between the crystals during solidification. This reduces the tendency towards casting errors. Fewer inclusions of magnesium, silicon or oxygen compounds have a favorable influence on the microporosity of the cast iron and promote a uniform solidification in the form. A lower microporosity is also advantageous for the interaction of the melt with the molding material mixture or with the sand from which the mold is formed. This makes the surface of the cast iron product cleaner and more uniform, i.e. H. there are fewer surface defects. This makes it easier to machine the surface of the cast iron product.
Die Figuren 1 und 2 zeigen eine Mikroskopaufnahme eines Kugelgraphitpartikels mit darin einem ungelösten Kern eines Impfmittels. Figur 2 zeigt eine Vergrösserung aus dem zentralen Bereich des Partikels von Figur 1. Der Kugelgraphitpartikel wurde aus einer Schmelze erhalten, die geimpft wurde mit einer Verbindung von Eisen, Silicium und Lanthan. Die Analyse des Kerns des Kugelgraphitpartikels ergab folgende Zusammensetzung: 41 ,7% La, 47,2% S, 9,1% Mg und 1,7% Si. Hiermit wird gezeigt, dass die schlechte Löslichkeit der in geringen Mengen zugeführten Verbindungen oder Mischungen, die Oxysulfiden bilden, einen günstigen Einfluss auf die Bildung von Kugelgraphitpartikeln und auf die Gusseigenschaften hat.FIGS. 1 and 2 show a microscope image of a spheroidal graphite particle with an undissolved core of a vaccine therein. Figure 2 shows an enlargement from the central area of the particle of Figure 1. The spheroidal graphite particle was obtained from a melt which was inoculated with a compound of iron, silicon and lanthanum. The analysis of the core of the spheroidal graphite particle showed the following composition: 41.7% La, 47.2% S, 9.1% Mg and 1.7% Si. This shows that the poor solubility of the compounds or mixtures which form small amounts and which form oxysulfides has a favorable influence on the formation of spheroidal graphite particles and on the casting properties.
Die Kugelgraphit-Gusseisenprodukte, die nach diesem Verfahren hergestellt werden, zeichnen sich aus durch eine hohe Reinheit bei relativ günstigen Herstellungskosten. Es müssen weniger Schlacken entsorgt oder rezykliert werden und die Dosierung der Impfmittel kann erheblich kleiner ausgelegt werden. Der Aufwand für Messung und Regelung des Giessprozesses, insbesondere der apparative Aufwand für die Analyse der Schmelze kann, weil der Prozess stabiler und besser reproduzierbar ist, erheblich reduziert werden. Das Mengenverhältnis der zugegebenen Fremdkörper kann zwischen Vorbehandlung und Impfmittel angepasst werden. Durch die gegenseitige Anpassung zwischen Vorbehandlung und Impfmittelzugabe kann sowohl die Keimbildung in der Schmelze als auch die Erstarrung in der Form aufeinander abgestimmt werden. Durch die richtige Wahl der Art und der Mengen der Fremdkörper kann unter Umständen auf eine Zugabe beim Abgiessen in die Form verzichtet werden. Gusseisen mit Kugelgraphit (GJS) zeichnet sich aus durch mechanische Eigenschaften, die den mechanischen Eigenschaften von Stahlguss sehr nahe kommen. The spheroidal graphite cast iron products that are manufactured by this process are characterized by a high degree of purity at relatively low manufacturing costs. Less slag has to be disposed of or recycled and the dosage of the inoculants can be made significantly smaller. The effort for measuring and controlling the casting process, in particular the equipment for analyzing the melt, can be considerably reduced because the process is more stable and more reproducible. The quantity ratio of the foreign bodies added can be adjusted between pretreatment and vaccine. The mutual adaptation between pretreatment and the addition of inoculant allows both the nucleation in the melt and the solidification in the mold to be coordinated. With the right choice of the type and the amount of foreign bodies, it may be possible to dispense with an addition when pouring into the mold. Spheroidal graphite cast iron (GJS) is characterized by mechanical properties that come very close to the mechanical properties of cast steel.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Kugelgraphit-Gusseisen umfassend zumindest die Verfahrensschritte Vorbehandlung mit reinem Magnesium in einem Konverter und Impfmittelzugabe beim Abgiessen in die Form, dadurch gekennzeichnet, dass die Löslichkeit der in der Vorbehandlung und in der Impfmittelzugabe gebildeten Substanzen einstellbar ist.1. A process for producing spheroidal graphite cast iron comprising at least the process steps pretreatment with pure magnesium in a converter and inoculant addition when pouring into the mold, characterized in that the solubility of the substances formed in the pretreatment and in the inoculant addition is adjustable.
2. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach dem Anspruch 1 , dadurch gekennzeichnet, dass die Vorbehandlung mit einer Mischung oder einer2. A method for producing spheroidal graphite cast iron according to claim 1, characterized in that the pretreatment with a mixture or
Verbindung von reinem metallischen Magnesium mit einem oder mehreren Metallen aus den Gruppen lla und lila des Periodensystems und mit Schwefel durchgeführt wird.Connection of pure metallic magnesium with one or more metals from groups lla and purple of the periodic table and with sulfur is carried out.
3. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach dem Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Menge eines auf FeSi oder CaSi basierenden Impfmittels, das beim Abgiessen in die Form zugegeben wird, wesentlich kleiner, vorzugsweise viermal kleiner, ist, als die in der Vorbehandlung mit Magnesium eingesetzten Menge der Oxysulfiden bildenden Verbindungen oder Mischungen.3. A process for the production of spheroidal graphite cast iron according to claim 1 or 2, characterized in that the amount of a FeSi or CaSi-based inoculant which is added to the mold when poured is substantially smaller, preferably four times smaller, than that amount of oxysulfide-forming compounds or mixtures used in the pretreatment with magnesium.
4. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Vorbehandlung mit einer Mischung oder einer Verbindung von reinem metallischen Magnesium mit Schwefel und mit Ca, Ba, La oder seltenen Erden, wobei die Mischung oder die Verbindung durch Reaktion mit der Metallschmelze Oxysulfiden bildet, durchgeführt wird.4. A process for producing spheroidal graphite cast iron according to one of claims 1 to 3, characterized in that the pretreatment with a mixture or a compound of pure metallic magnesium with sulfur and with Ca, Ba, La or rare earths, the mixture or the compound forms oxysulfides by reaction with the molten metal.
5. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass in der nachfolgenden5. A method for producing spheroidal graphite cast iron according to one of claims 1 to 4, characterized in that in the following
Impfmittelzugabe das auf FeSi oder CaSi basierende Impfmittel Mg, Ca, Ba, Au, Ge, Bi, La, oder seltene Erden enthält.Vaccine addition the FeSi or CaSi based vaccine Mg, Ca, Ba, Au, Contains Ge, Bi, La, or rare earths.
6. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die gebildeten Oxysulfide eine Korngrösse von 0,001 bis 0,03 mm aufweisen.6. A method for producing spheroidal graphite cast iron according to one of claims 1 to 5, characterized in that the oxysulfides formed have a grain size of 0.001 to 0.03 mm.
7. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die gebildeten Oxysulfide ein spezifisches Gewicht von 4000 bis 6000 kg/m3 aufweisen.7. A process for producing spheroidal graphite cast iron according to one of claims 1 to 6, characterized in that the oxysulfides formed have a specific weight of 4000 to 6000 kg / m 3 .
8. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die gebildeten Oxysulfide einen Schmelzpunkt von 1250 bis 1550 °C aufweisen.8. A method for producing spheroidal graphite cast iron according to one of claims 1 to 7, characterized in that the oxysulfides formed have a melting point of 1250 to 1550 ° C.
9. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der9. Process for the production of spheroidal graphite cast iron according to one of the
Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die spezifische Keimzahl der gebildeten Oxysulfiden zwischen 60 und 1200 mm"2 beträgt.Claims 1 to 8, characterized in that the specific bacterial count of the oxysulfides formed is between 60 and 1200 mm "2 .
10. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die zur Vorbehandlung verwendeten Verbindungen oder Mischungen getrennt vom reinen Magnesium, mit dem Magnesium verbunden oder legiert, oder als Draht, als Granulat oder in Form eines Sandwiches im Magnesium eingebettet in die Schmelze im Konverter eingebracht werden.10. A process for the production of spheroidal graphite cast iron according to one of claims 1 to 9, characterized in that the compounds or mixtures used for the pretreatment are separated from the pure magnesium, bonded or alloyed with the magnesium, or as wire, as granules or in the form of a Sandwiches embedded in magnesium can be introduced into the melt in the converter.
11. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Menge und die Art der beim Abgiessen in die Form eingebrachten Impfmittel angepasst werden an die Menge und die Art der bei der Vorbehandlung im Konverter eingebrachten Oxysulfiden bildenden Verbindungen oder Mischungen mit Magnesium und Schwefel. 11. A process for the production of spheroidal graphite cast iron according to one of claims 1 to 10, characterized in that the amount and the type of inoculants introduced into the mold during the pouring are adapted to the amount and the type of oxysulfides introduced in the converter during the pretreatment forming compounds or mixtures with magnesium and sulfur.
12. Verfahren zur Herstellung von Kugelgraphit-Gusseisen nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die Menge und die Art der bei der Vorbehandlung im Konverter eingebrachten Verbindungen oder Mischungen derart gewählt wird, dass auf eine Zugabe von Impfmittel beim Abgiessen in die Form verzichtet werden kann. 12. A process for producing spheroidal graphite cast iron according to one of claims 1 to 11, characterized in that the amount and the type of the compounds or mixtures introduced in the pretreatment in the converter is selected such that an addition of inoculant when pouring into the Form can be dispensed with.
EP01927562A 2000-05-26 2001-05-16 Method for producing spheroidal graphite cast iron Expired - Lifetime EP1283913B1 (en)

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DE10025940A DE10025940A1 (en) 2000-05-26 2000-05-26 Process for the production of spheroidal graphite cast iron
DE10025940 2000-05-26
PCT/CH2001/000303 WO2001090425A1 (en) 2000-05-26 2001-05-16 Method for producing spheroidal graphite cast iron

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US3871870A (en) * 1973-05-01 1975-03-18 Nippon Kokan Kk Method of adding rare earth metals or their alloys into liquid steel
DE3801917A1 (en) * 1988-01-23 1989-08-03 Metallgesellschaft Ag METHOD FOR PRODUCING CAST IRON WITH BALL GRAPHITE
US5100612A (en) * 1989-06-21 1992-03-31 501 Hitachi Metals, Ltd. Spheroidal graphite cast iron
DE3924558C1 (en) * 1989-07-25 1990-11-22 Skw Trostberg Ag, 8223 Trostberg, De
CH679987A5 (en) * 1989-11-28 1992-05-29 Fischer Ag Georg
SE501003C2 (en) * 1990-10-15 1994-10-17 Sintercast Ab Process for the production of iron
SE469712B (en) * 1990-10-15 1993-08-30 Sintercast Ltd PROCEDURES FOR PREPARING THE IRON WITH COMPACT GRAPHITE
NO306169B1 (en) * 1997-12-08 1999-09-27 Elkem Materials Cast iron grafting agent and method of making grafting agent
SE512201C2 (en) * 1998-03-06 2000-02-14 Sintercast Ab Process for the preparation of Mg-treated iron with improved processability

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