EP0546351A2 - Cored wire containing a passivated pyrophoric metal and its application - Google Patents

Cored wire containing a passivated pyrophoric metal and its application Download PDF

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Publication number
EP0546351A2
EP0546351A2 EP92119560A EP92119560A EP0546351A2 EP 0546351 A2 EP0546351 A2 EP 0546351A2 EP 92119560 A EP92119560 A EP 92119560A EP 92119560 A EP92119560 A EP 92119560A EP 0546351 A2 EP0546351 A2 EP 0546351A2
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EP
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Prior art keywords
weight
cored wire
metal
passivated
magnesium
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EP92119560A
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German (de)
French (fr)
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EP0546351B1 (en
EP0546351A3 (en
Inventor
Detlef Dr. Missol
Friedrich Wolfsgruber
Helmut Dr. Lischka
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Evonik Operations GmbH
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SKW Trostberg AG
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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
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing

Definitions

  • the present invention relates to the use of cored wires with a filling in the form of passivated, reactive metals.
  • Pyrophoric metals such as magnesium, calcium, aluminum and corresponding alloys thereof, in particular in finely divided form, pose particular problems in their handling and use.
  • the metals are used in the finely divided form for treatment, such as for the deoxidation of iron and steel melts, for the desulphurization of pig iron melts, for the production of certain alloys and others.
  • published patent application DE 39 08 815 A1 describes a process for passivating pyrophoric metals, in particular magnesium, with 0.5 to 5% by weight of an s-triazine and / or guanidine derivative as a passivating agent, based on the weight of the metal , described.
  • Such passivated fine-particle metals are characterized by their favorable burning behavior and are therefore particularly suitable as treatment agents for metallurgical melts, e.g. in the desulfurization of pig iron.
  • DE 39 08 815 is hereby incorporated by reference into the present disclosure.
  • patent specification DE 39 24 558 C1 describes an agent in the form of a cored wire and a method for its production, the use of which consists in treating cast iron melts with a magnesium-containing silicon alloy.
  • the advantage of the flux cored wire described can be seen in the shifting of the excretion form of the cast iron carbon in the direction of spheroidal graphite by alloying 5-30% by weight of pure magnesium and 0.1-5% by weight of rare earth metals, as well as in the reduction of the process steps desulfurization, magnesium treatment and Inoculating cast iron melts on a single treatment measure to be carried out simultaneously.
  • the present invention was based on the object of using a cored wire with a content enable pyrophoric metal for the treatment of molten metals in an economical manner. Further objects of the invention are evident from the description below.
  • a finely divided pyrophoric metal such as magnesium is used, which has been coated with a passivating agent based on organic nitrogen compounds, preferably organic NCN compounds from the series of s-triazines and / or guanidine derivatives.
  • a passivating agent based on organic nitrogen compounds, preferably organic NCN compounds from the series of s-triazines and / or guanidine derivatives.
  • Preference is given to passivating the pyrophoric metal in particular magnesium, melamine or melamine cyanurate, guanyl urea or guanyl urea phosphate.
  • Cyanoguanidine (dicyandiamide) is particularly preferably used as a passivating agent.
  • the passivating agent is used in an amount of 0.5 to 5% by weight, preferably 3% by weight, based on the weight of the pyrophoric metal, and applied to the metal with the aid of an adhesion promoter. Viscous mineral oils, vegetable oils or preferably silicone oils are used as adhesion promoters. Such adhesion promoters are generally used in an amount of 0.1 to 0.5% by weight, based on the metal to be coated (see published patent application DE 39 08 815 A1).
  • the particle size of the passivating agent is 5 to 60 ⁇ m, preferably less than 10 ⁇ m.
  • wires filled with the passivated metal particles described above has the advantage over the wires filled with non-passivated pyrophoric metals that the yield of reactive component is higher and incorrect treatment and rejects are excluded.
  • cored wires also contribute to operational and occupational safety and environmental protection, since after the winding process has ended they neither glow nor burn and do not release any, possibly harmful, metal oxides into the environment.
  • additional components in the form of alloys, metals or other agents can be added to the passivated pyrophoric metal.
  • additional components are, for example, one or more alloys from the series calcium silicon, ferrosilicon, rare earth metals-containing ferrosilicon, magnesium and / or calcium-containing ferrosilicon, ferromanganese, the metals copper, manganese and tin.
  • Calcium carbide, carbon and silicon dioxide can optionally also be added to the passivated pyrophoric metal as further components.
  • the proportions of the additional filler components in a mixture with the passivated pyrophoric metal can be up to 90% by weight.
  • a preferred wire filling which in addition to passivated magnesium contains further treatment agents for the purpose of desulfurization and inoculation, is, for example, a mixture of 40 to 60% by weight of passivated magnesium with 60 to 40% by weight of ferrosilicon, optionally with a content of 0.3 to 1.3% by weight of rare earth metals.
  • a wire fill consists of 49% by weight of magnesium and 51% by weight of ferrosilicon, optionally with a content of 0.5 to 1% by weight, preferably 0.9%. %, Rare earth metal.
  • a cored wire that alloys the treated metal at the same time contains, in addition to the desulfurizing and inoculating components, alloying elements such as copper, manganese or tin in appropriate proportions.
  • the wire filling can also contain non-metallic components, e.g. Calcium carbide, carbon or silicon dioxide. These components are used for desulfurization, carburization or as a filler to dampen the reaction. Their amount generally depends on the sulfur content of the base iron, the amount of carbon required or the intended degree of reaction damping.
  • non-metallic components e.g. Calcium carbide, carbon or silicon dioxide.
  • the particle size of the passivated pyrophoric metal is preferably between 0.1 to 2 mm and is particularly preferably 0.2 to about 0.7 mm.
  • the additional components are in a particle size of preferably 0.05 to 2.0 mm, particularly preferably 0.1 to 1.6 mm.
  • a typical cored wire sheathing consists of folded steel, rare copper tape, the wall of which is a thickness of 0.25 or 0.4 mm; Such cored wires with a total diameter of 5.9 and 13 mm are used.
  • the cored wire used in accordance with the invention is characterized by a safe application, a high yield of the reactive component and by being environmentally friendly. Due to the constant burn-off conditions and the good reproducibility of the reactive component, there is a significant quality improvement in the treated metal melts. For example, in the manufacture of spheroidal graphite cast iron using a cored wire filled with passivated magnesium particles, this has less oxidized magnesium on the bath surface after the treatment has ended. As a result, the reject rate caused by surface defects (Dross) is significantly reduced.
  • Magnesium powder (99.8% Mg) with a particle size of 0.2 to 0.7 mm was mixed with 0.3% by weight of silicone oil and passivated with 3% by weight of dicyandiamide with a particle size of 98% ⁇ 10 ⁇ m by coating.
  • the magnesium pretreated in this way is packed in a cored wire with the following key figures: Wire diameter 9 mm Wire weight 178 g / m Filling weight 65 g / m Fill factor 36.5%
  • a base iron of the following analysis was melted in the induction crucible furnace: 3.75 wt% carbon 2.40% by weight silicon 0.18% by weight of manganese 0.014 wt% phosphorus 0.008% by weight sulfur The iron was treated by winding 18 m of the wire to obtain the results shown in Table 1.
  • Magnesium powder (99.8% Mg) was passivated as described in Example 1. 40 parts by weight of the passivated magnesium were then mixed with 51 parts by weight of ferrosilicon (75% Si) with a particle size of 0.2 to 0.7 mm and 9 parts by weight with rare earth metal-containing ferrosilicon (FeSiSE 36) with a particle size of 0 , 01 to 1 mm mixed and packed in a cored wire, which has the following characteristics: Wire diameter 9 mm Wire weight 206 g / m Filling weight 94 g / m Fill factor 46% Magnesium content 36 g / m Silicon content 30 g / m SE content 3 g / m
  • the precipitated graphite showed a portion of> 90% in spherical form in a cast Y2 sample (25 mm).
  • the number of Spärolites of 250 balls / mm2 corresponded to the inoculation power of this type of wire.

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  • 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)
  • Metal Extraction Processes (AREA)
  • Wire Bonding (AREA)
  • Luminescent Compositions (AREA)
  • Resistance Heating (AREA)
  • Conductive Materials (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Ropes Or Cables (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)

Abstract

The invention concerns a cored wire comprising a metal tube and a filling of magnesium or other pyrophoric metals passivated with from 0.5 to 5% by weight of organic nitrogen compounds. As the passivating agent, compounds from the series of the s-triazine and/or guanidine derivatives, preferably from 2 to 5% by weight of dicyandiamide, applied by means of an adhesion promoter, are preferred. The wires used in accordance with the invention serve to produce cast iron with spheroidal and vermicular graphite, to desulphurize pig iron melts or to produce metal alloys.

Description

Die vorliegende Erfindung betrifft die Verwendung von Fülldrähten mit einer Füllung in Form von passivierten, reaktiven Metallen.The present invention relates to the use of cored wires with a filling in the form of passivated, reactive metals.

Pyrophore Metalle, wie Magnesium, Calcium, Aluminium sowie entsprechende Legierungen hiervon, insbesondere in feinteiliger Form, werfen besondere Probleme bei ihrer Handhabung und Anwendung auf. Angewendet werden die Metalle in der feinteiligen Form zum Behandeln, wie zur Desoxidation von Eisen- und Stahlschmelzen, zur Entschwefelung von Roheisenschmelzen, zur Herstellung bestimmter Legierungen u.a.Pyrophoric metals, such as magnesium, calcium, aluminum and corresponding alloys thereof, in particular in finely divided form, pose particular problems in their handling and use. The metals are used in the finely divided form for treatment, such as for the deoxidation of iron and steel melts, for the desulphurization of pig iron melts, for the production of certain alloys and others.

Es ist aus der US-PS 4 209 325 bzw. US-PS 3 998 625 bereits bekannt, pyrophore Metalle durch Zugabe von 10 bis 50 Gew.% Kalk, Aluminiumoxid, SiO₂-Stäuben oder metallurgischen Schlacken zu verdünnen, um ihre Entzündbarkeit zu vermindern.It is already known from US Pat. No. 4,209,325 or US Pat. No. 3,998,625 to dilute pyrophoric metals by adding 10 to 50% by weight of lime, aluminum oxide, SiO 2 dusts or metallurgical slags in order to reduce their flammability .

Bei der Beschichtung der pyrophoren Metalle mit Salzschmelzen, wobei vorwiegend Alkali- oder Erdalkalichloride verwendet werden (US-PS 3 881 913, US-PS 4 186 000 oder US-PS 4 279 641), erfordern die chlorhaltigen Salze besondere Maßnahmen zum Schutz der Anlagenteile und der Umwelt.When coating the pyrophoric metals with molten salts, predominantly alkali metal or alkaline earth metal chlorides being used (US Pat. No. 3,881,913, US Pat. No. 4,186,000 or US Pat. No. 4,279,641), the chlorine-containing salts require special measures to protect the plant parts and the environment.

Schließlich wird in der Offenlegungsschrift DE 39 08 815 A1 ein Verfahren zur Passivierung von pyrophoren Metallen, insbesondere Magnesium, mit 0,5 bis 5 Gew.% eines s-Triazin- und/oder Guanidin-Derivates als Passivierungsmittel, bezogen auf das Gewicht des Metalles, beschrieben. Derart passivierte feinteilige Metalle zeichnen sich durch ihr günstiges Abbrandverhalten aus und eignen sich deshalb besonders als Behandlungsmittel für metallurgische Schmelzen, z.B. bei der Entschwefelung von Roheisen. DE 39 08 815 wird hiermit als Referenz in die vorliegende Offenbarung aufgenommen.Finally, published patent application DE 39 08 815 A1 describes a process for passivating pyrophoric metals, in particular magnesium, with 0.5 to 5% by weight of an s-triazine and / or guanidine derivative as a passivating agent, based on the weight of the metal , described. Such passivated fine-particle metals are characterized by their favorable burning behavior and are therefore particularly suitable as treatment agents for metallurgical melts, e.g. in the desulfurization of pig iron. DE 39 08 815 is hereby incorporated by reference into the present disclosure.

Für die Behandlung von Eisenschmelzen, z.B. in Gießereibetrieben, wurde in den letzten Jahren die Behandlung der Schmelzen mit Fülldrähten mit einer Füllung aus entsprechenden Bestandteilen eingeführt, und diese hat sich mittlerweile weitgehend durchgesetzt.For the treatment of molten iron, e.g. In foundries, the treatment of melts with cored wire with a filling of the corresponding components has been introduced in recent years, and this has now largely become established.

So beschreibt die Patentschrift DE 39 24 558 C1 ein Mittel in der Form eines Fülldrahtes und ein Verfahren zu seiner Herstellung, wobei dessen Verwendung in dem Behandeln von Gußeisenschmelzen mit einer Magnesium-enthaltenden Siliziumlegierung besteht. Der Vorteil des beschriebenen Fülldrahtes ist in der Verschiebung der Ausscheidungsform des Gußeisenkohlenstoffes in Richtung Kugelgraphitform durch Zulegieren von 5-30 Gew.% reinem Magnesium und 0,1-5 Gew.% Seltenerdmetalle zu sehen, sowie in der Reduzierung der Verfahrensschritte Entschwefelung, Magnesiumbehandeln und Impfen von Gußeisenschmelzen auf eine einzige, zeitgleich durchzuführende Behandlungsmaßnahme.For example, patent specification DE 39 24 558 C1 describes an agent in the form of a cored wire and a method for its production, the use of which consists in treating cast iron melts with a magnesium-containing silicon alloy. The advantage of the flux cored wire described can be seen in the shifting of the excretion form of the cast iron carbon in the direction of spheroidal graphite by alloying 5-30% by weight of pure magnesium and 0.1-5% by weight of rare earth metals, as well as in the reduction of the process steps desulfurization, magnesium treatment and Inoculating cast iron melts on a single treatment measure to be carried out simultaneously.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, die Verwendung eines Fülldrahtes mit einem Inhalt an pyrophorem Metall für die Behandlung von Metallschmelzen in wirtschaftlicher Weise zu ermöglichen. Weitere Ziele der Erfindung sind aus der nachfolgenden Beschreibung ersichtlich.The present invention was based on the object of using a cored wire with a content enable pyrophoric metal for the treatment of molten metals in an economical manner. Further objects of the invention are evident from the description below.

Gemäß der Erfindung verwendet man ein feinteiliges pyrophores Metall wie etwa Magnesium, das mit einem Passivierungsmittel auf Basis von organischen Stickstoffverbindungen, bevorzugt organischen NCN-Verbindungen aus der Reihe der s-Triazine und/oder Guanidin-Derivate, beschichtet worden ist. Bevorzugt wird für die Passivierung des pyrophoren Metalls, insbesondere von Magnesium, Melamin oder Melamincyanurat, Guanylharnstoff oder Guanylharnstoffphosphat verwendet. Besonders bevorzugt findet Cyanoguanidin (Dicyandiamid) als Passivierungsmittel Verwendung.According to the invention, a finely divided pyrophoric metal such as magnesium is used, which has been coated with a passivating agent based on organic nitrogen compounds, preferably organic NCN compounds from the series of s-triazines and / or guanidine derivatives. Preference is given to passivating the pyrophoric metal, in particular magnesium, melamine or melamine cyanurate, guanyl urea or guanyl urea phosphate. Cyanoguanidine (dicyandiamide) is particularly preferably used as a passivating agent.

Das Passivierungsmittel wird in einer Menge von 0,5 bis 5 Gew.%, vorzugsweise 3 Gew.%, bezogen auf das Gewicht des pyrophoren Metalls, eingesetzt und mit Hilfe eines Haftvermittlers auf das Metall aufgebracht. Als Haftvermittler werden viskose Mineralöle, pflanzliche Öle oder bevorzugt Siliconöle verwendet. Solche Haftvermittler werden im allgemeinen in einer Menge von 0,1 bis 0,5 Gew.%, bezogen auf das zu beschichtende Metall, eingesetzt (siehe Offenlegungsschrift DE 39 08 815 A1). Die Teilchengröße des Passivierungsmittels beträgt 5 bis 60 µm, vorzugsweise weniger als 10 µm.The passivating agent is used in an amount of 0.5 to 5% by weight, preferably 3% by weight, based on the weight of the pyrophoric metal, and applied to the metal with the aid of an adhesion promoter. Viscous mineral oils, vegetable oils or preferably silicone oils are used as adhesion promoters. Such adhesion promoters are generally used in an amount of 0.1 to 0.5% by weight, based on the metal to be coated (see published patent application DE 39 08 815 A1). The particle size of the passivating agent is 5 to 60 μm, preferably less than 10 μm.

Die Erfinder bemerkten, daß die Zugabe von reaktiven Metallen, wie z.B. Magnesium, zu Eisenschmelzen in Form eines Fülldrahtes den Nachteil hatte, daß dieser nach Beendigung des Einspulvorganges noch eine beträchtliche Strecke weiterbrannte, bevor er verlöschte. Dies wirkte sich negativ auf die Ausbeute an Behandlungsmittel aus und führte zu Fehlbehandlungen und Ausschuß. Daneben gaben diese Drähte Anlaß zu Unfällen und einer beträchtlichen Belästigung am Arbeitsplatz durch Metalloxide.The inventors noted that the addition of reactive metals, such as magnesium, to molten iron in the form of a cored wire had the disadvantage that it continued to burn a considerable distance after the winding-in process had ended before it extinguished. This had a negative effect on the yield of treatment agent and led to mistreatment and rejects. In addition, these wires have given rise to accidents and considerable exposure to metal oxides in the workplace.

Die erfindungsgemäße Verwendung von mit den oben beschriebenen passivierten Metallpartikeln gefüllten Drähten besitzt gegenüber den mit nichtpassivierten pyrophoren Metallen gefüllten Drähten den Vorteil, daß die Ausbeute an reaktiver Komponente höher ist und Fehlbehandlungen und Ausschuß ausgeschlossen werden. Ferner tragen derartige Fülldrähte zur Betriebs- und Arbeitssicherheit sowie zum Umweltschutz bei, da sie nach Beendigung des Einspulvorganges weder nachglimmen noch nachbrennen und keine, ggf. schädlichen, Metalloxide in die Umgebung abgeben.The use according to the invention of wires filled with the passivated metal particles described above has the advantage over the wires filled with non-passivated pyrophoric metals that the yield of reactive component is higher and incorrect treatment and rejects are excluded. Such cored wires also contribute to operational and occupational safety and environmental protection, since after the winding process has ended they neither glow nor burn and do not release any, possibly harmful, metal oxides into the environment.

Für die erfindungsgemäße Verwendung können dem passivierten pyrophoren Metall zusätzliche Komponenten in Form von Legierungen, Metallen oder anderen Mitteln zugesetzt werden. Solche zusätzlichen Komponenten sind z.B. eine oder mehrere Legierungen aus der Reihe Calciumsilicium, Ferrosilicium, Seltenerdmetalle enthaltendes Ferrosilicium, Magnesium und/oder Calcium enthaltendes Ferrosilicium, Ferromangan, die Metalle Kupfer, Mangan und Zinn. Als weitere Komponenten können dem passivierten pyrophoren Metall gegebenenfalls auch Calciumcarbid, Kohlenstoff und Siliciumdioxid beigemischt werden. Die Anteile der zusätzlichen Füllstoffkomponenten im Gemisch mit dem passivierten pyrophoren Metall können bis zu 90 Gew.% betragen. Eine bevorzugte Drahtfüllung, die neben passiviertem Magnesium noch weiteres Behandlungsmittel zum Zwecke des Entschwefelns und Impfens enthält, stellt beispielsweise ein Gemisch von 40 bis 60 Gew.% passiviertes Magnesium mit 60 bis 40 Gew.% Ferrosilicium, gegebenenfalls mit einem Gehalt von 0,3 bis 1,3 Gew.% an Seltenerdmetallen, dar. Besonders bevorzugt besteht eine derartige Drahtfüllung aus 49 Gew.% Magnesium und 51 Gew.% Ferrosilicium, gegebenenfalls mit einem Gehalt von 0,5 bis 1 Gew.%, vorzugsweise 0,9 Gew.%, Seltenerdmetall.For the use according to the invention, additional components in the form of alloys, metals or other agents can be added to the passivated pyrophoric metal. Such additional components are, for example, one or more alloys from the series calcium silicon, ferrosilicon, rare earth metals-containing ferrosilicon, magnesium and / or calcium-containing ferrosilicon, ferromanganese, the metals copper, manganese and tin. Calcium carbide, carbon and silicon dioxide can optionally also be added to the passivated pyrophoric metal as further components. The proportions of the additional filler components in a mixture with the passivated pyrophoric metal can be up to 90% by weight. A preferred wire filling, which in addition to passivated magnesium contains further treatment agents for the purpose of desulfurization and inoculation, is, for example, a mixture of 40 to 60% by weight of passivated magnesium with 60 to 40% by weight of ferrosilicon, optionally with a content of 0.3 to 1.3% by weight of rare earth metals. Particularly preferably, such a wire fill consists of 49% by weight of magnesium and 51% by weight of ferrosilicon, optionally with a content of 0.5 to 1% by weight, preferably 0.9%. %, Rare earth metal.

Ein Fülldraht, der gleichzeitig das behandelte Metall legiert, enthält neben den entschwefelnden und impfenden Bestandteilen noch legierende Elemente wie Kupfer, Mangan oder Zinn in entsprechenden Anteilen.A cored wire that alloys the treated metal at the same time contains, in addition to the desulfurizing and inoculating components, alloying elements such as copper, manganese or tin in appropriate proportions.

Neben den zu verwendenden metallischen Bestandteilen kann die Drahtfüllung auch nichtmetallische Komponenten enthalten, wie z.B. Calciumcarbid, Kohlenstoff oder Siliciumdioxid. Diese Bestandteile dienen zur Entschwefelung, dem Aufkohlen bzw. als Füllstoff zur Dämpfung der Reaktion. Deren Menge richtet sich im allgemeinen nach dem Schwefelgehalt des Basiseisens, dem benötigten Kohlenstoffanteil bzw. dem beabsichtigten Grad der Reaktionsdämpfung.In addition to the metallic components to be used, the wire filling can also contain non-metallic components, e.g. Calcium carbide, carbon or silicon dioxide. These components are used for desulfurization, carburization or as a filler to dampen the reaction. Their amount generally depends on the sulfur content of the base iron, the amount of carbon required or the intended degree of reaction damping.

Die gleichzeitige Anwesenheit solcher Behandlungskomponenten erlaubt die Verwendung des Fülldrahtes, um u.a. das Gußeisen in einem Arbeitsgang auf das gewünschte Gefüge bzw. die gewünschte Zusammensetzung einzustellen.The simultaneous presence of such treatment components allows the use of the cored wire to e.g. adjust the cast iron to the desired structure or composition in one operation.

Die Teilchengröße des passivierten pyrophoren Metalls liegt vorzugsweise zwischen 0,1 bis 2 mm und beträgt besonders vorzugsweise 0,2 bis etwa 0,7 mm. Die zusätzlichen Komponenten liegen in einer Teilchengröße von vorzugsweise 0,05 bis 2,0 mm, besonders vorzugsweise von 0,1 bis 1,6 mm, vor.The particle size of the passivated pyrophoric metal is preferably between 0.1 to 2 mm and is particularly preferably 0.2 to about 0.7 mm. The additional components are in a particle size of preferably 0.05 to 2.0 mm, particularly preferably 0.1 to 1.6 mm.

Eine typische Fülldrahtumhüllung besteht aus gefalztem Stahl-, seltener Kupferband, dessen Wandung eine Stärke von 0,25 oder 0,4 mm aufweist; zur Anwendung gelangen derartige Fülldrähte mit Gesamtdurchmessern von 5,9 und 13 mm.A typical cored wire sheathing consists of folded steel, rare copper tape, the wall of which is a thickness of 0.25 or 0.4 mm; Such cored wires with a total diameter of 5.9 and 13 mm are used.

Der erfindungsgemäß verwendete Fülldraht zeichnet sich durch sichere Anwendungsmöglichkeit, hohe Ausbeute an der reaktiven Komponente sowie durch Umweltfreundlichkeit aus. Aufgrund der konstanten Abbrandverhältnisse und der guten Reproduzierbarkeit der reaktiven Komponente ergibt sich eine bedeutende Qualitätsverbesserung bei den behandelten Metallschmelzen. Zum Beispiel weist bei der Herstellung von Gußeisen mit Kugelgraphit unter Verwendung eines mit passivierten Magnesiumpartikeln gefüllten Fülldrahtes dieses nach beendeter Behandlung weniger oxidiertes Magnesium an der Badoberfläche auf. Dadurch wird der Ausschußanteil, verursacht durch Oberflächenfehler (Dross), deutlich reduziert.The cored wire used in accordance with the invention is characterized by a safe application, a high yield of the reactive component and by being environmentally friendly. Due to the constant burn-off conditions and the good reproducibility of the reactive component, there is a significant quality improvement in the treated metal melts. For example, in the manufacture of spheroidal graphite cast iron using a cored wire filled with passivated magnesium particles, this has less oxidized magnesium on the bath surface after the treatment has ended. As a result, the reject rate caused by surface defects (Dross) is significantly reduced.

Die nachfolgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.

Beispiel 1example 1

Magnesiumpulver (99,8% Mg) einer Teilchengröße von 0,2 bis 0,7 mm wurde mit 0,3 Gew.% Siliconöl versetzt und mit 3 Gew.% Dicyandiamid einer Teilchengröße von 98% < 10 µm durch Beschichten passiviert. Das so vorbehandelte Magnesium wird in einen Fülldraht verpackt, der folgende Kennzahlen besitzt: Drahtdurchmesser 9 mm Drahtgewicht 178 g/m Füllgewicht 65 g/m Füllfaktor 36,5 % Magnesiumgehalt 63 g/m Magnesium powder (99.8% Mg) with a particle size of 0.2 to 0.7 mm was mixed with 0.3% by weight of silicone oil and passivated with 3% by weight of dicyandiamide with a particle size of 98% <10 μm by coating. The magnesium pretreated in this way is packed in a cored wire with the following key figures: Wire diameter 9 mm Wire weight 178 g / m Filling weight 65 g / m Fill factor 36.5% Magnesium content 63 g / m

Im Induktionstiegelofen wurde ein Basiseisen folgender Analyse erschmolzen:
3,75 Gew.% Kohlenstoff
2,40 Gew.% Silicium
0,18 Gew.% Mangan
0,014 Gew.% Phosphor
0,008 Gew.% Schwefel
Durch Einspulen von 18 m des Drahtes wurde das Eisen behandelt, wobei die aus der Tabelle 1 hervorgehenden Ergebnisse erhalten wurden.A base iron of the following analysis was melted in the induction crucible furnace:
3.75 wt% carbon
2.40% by weight silicon
0.18% by weight of manganese
0.014 wt% phosphorus
0.008% by weight sulfur
The iron was treated by winding 18 m of the wire to obtain the results shown in Table 1.

Beispiel 2Example 2

Magnesiumpulver (99,8% Mg) wurde, wie in Beispiel 1 beschrieben, passiviert. Anschließend wurden 40 Gew.-Teile des passivierten Magnesiums mit 51 Gew. -Teilen Ferrosilicium (75% Si) einer Teilchengröße von 0,2 bis 0,7 mm und 9 Gew.-Teilen Seltenerdmetall enthaltendes Ferrosilicium (FeSiSE 36) einer Teilchengröße von 0,01 bis 1 mm gemischt und in einen Fülldraht verpackt, der folgende Kenndaten besitzt: Drahtdurchmesser 9 mm Drahtgewicht 206 g/m Füllgewicht 94 g/m Füllfaktor 46 % Magnesiumgehalt 36 g/m Siliciumgehalt 30 g/m SE-Gehalt 3 g/m Magnesium powder (99.8% Mg) was passivated as described in Example 1. 40 parts by weight of the passivated magnesium were then mixed with 51 parts by weight of ferrosilicon (75% Si) with a particle size of 0.2 to 0.7 mm and 9 parts by weight with rare earth metal-containing ferrosilicon (FeSiSE 36) with a particle size of 0 , 01 to 1 mm mixed and packed in a cored wire, which has the following characteristics: Wire diameter 9 mm Wire weight 206 g / m Filling weight 94 g / m Fill factor 46% Magnesium content 36 g / m Silicon content 30 g / m SE content 3 g / m

Vorentschwefeltes Kupolofeneisen mit folgender Analyse:
3,80 Gew.% Kohlenstoff
2,25 Gew.% Silicium
0,50 Gew.% Mangan
0,04 Gew.% Phosphor
0,012 Gew.% Schwefel
wurde durch Einspulen von 31 m des vorgenannten Drahtes behandelt. Die erhaltenen Ergebnisse sind in Tabelle 2 zusammengestellt. Tabelle 1 Behandlung Nr. 1 2 3 4 5 6 Basiseisen (kg) 1000 1000 1000 1000 1000 1000 Drahtmenge (m) 18 18 18 18 18 18 Einspulgeschwindigkeit (m/min) 35 35 35 35 35 35 Temperatur der Schmelze ( C) 1497 1506 1508 1498 1502 1504 Schwefelgehalt nach der Behandlung (% S) 0,004 0,003 0,003 0,004 0,003 0,003 eingebrachtes Magnesium (% Mg) 0,113 0,113 0,113 0,113 0,113 0,113 Rest-Magnesium (%) 0,042 0,040 0,039 0,041 0,040 0,039 Magnesium-Ausbeute 37 35 35 36 35 35 Anteil an Kugelgraphit (%) > 90 > 90 > 90 > 90 > 90 > 90 Sphärolite pro mm² 100--200 100- 100--200 -200 100--200 100--200 100--200 Pre-desulfurized cupola furnace with the following analysis:
3.80 wt% carbon
2.25% by weight silicon
0.50% by weight of manganese
0.04% by weight phosphorus
0.012% by weight sulfur
was treated by winding 31 m of the aforementioned wire. The results obtained are shown in Table 2. Table 1 Treatment no. 1 2nd 3rd 4th 5 6 Base iron (kg) 1000 1000 1000 1000 1000 1000 Amount of wire (m) 18th 18th 18th 18th 18th 18th Winding speed (m / min) 35 35 35 35 35 35 Melt temperature (C) 1497 1506 1508 1498 1502 1504 Sulfur content after treatment (% S) 0.004 0.003 0.003 0.004 0.003 0.003 Magnesium introduced (% Mg) 0.113 0.113 0.113 0.113 0.113 0.113 Residual magnesium (%) 0.042 0.040 0.039 0.041 0.040 0.039 Magnesium yield 37 35 35 36 35 35 Spherical graphite content (%) > 90 > 90 > 90 > 90 > 90 > 90 Spherolite per mm² 100-200 100-100-200 -200 100-200 100-200 100-200

Die Graphitausscheidung in der abgegossenen Y2-Probe (25 mm) zeigte einen Anteil an Kugelgraphit von über 90%. Die Zahl an Späroliten von 100 bis 200 Kugeln pro mm² entsprach dem erwarteten Effekt der Behandlung vor der Sekundärimpfung. Tabelle 2 Behandlung Nr. 1 2 3 4 Basiseisen (kg) 1000 1000 1000 1000 Drahtmenge (m) 31 31 31 31 Einspulgeschwindigkeit 28 28 28 28 Temperatur der Schmelze ( C) 1478 1485 1484 1480 Schwefelgehalt nach der Behandlung (% S) 0,009 0,008 0,008 0,008 eingebrachtes Magnesium (% Mg) 0,112 0,112 0,112 0,112 Rest-Magnesium (%) 0,044 0,046 0,046 0,045 Magnesium-Ausbeute (%) 39 41 41 40 Anteil an Kugelgraphit (%) > 90 > 90 > 90 > 90 Sphärolite pro mm² (Y2) 250 250 250 250 The graphite excretion in the cast Y2 sample (25 mm) showed a proportion of spheroidal graphite of over 90%. The number of Sparolites from 100 to 200 balls per mm² corresponded to the expected effect of the treatment before the secondary vaccination. Table 2 Treatment no. 1 2nd 3rd 4th Base iron (kg) 1000 1000 1000 1000 Amount of wire (m) 31 31 31 31 Winding speed 28 28 28 28 Melt temperature (C) 1478 1485 1484 1480 Sulfur content after treatment (% S) 0.009 0.008 0.008 0.008 Magnesium introduced (% Mg) 0.112 0.112 0.112 0.112 Residual magnesium (%) 0.044 0.046 0.046 0.045 Magnesium yield (%) 39 41 41 40 Spherical graphite content (%) > 90 > 90 > 90 > 90 Spherolite per mm² (Y2) 250 250 250 250

Der ausgeschiedene Graphit zeigte in einer abgegossenen Y2-Probe (25 mm) einen Anteil von > 90% in Kugelform. Die Anzahl an Späroliten von 250 Kugeln/mm² entsprach der Impfkraft dieses Drahttypes.The precipitated graphite showed a portion of> 90% in spherical form in a cast Y2 sample (25 mm). The number of Spärolites of 250 balls / mm² corresponded to the inoculation power of this type of wire.

Claims (9)

Verwendung eines mit 0,5 bis 5 Gew.% einer organischen Stickstoffverbindung auf Basis eines mit einem s-Triazin und/oder Guanidin-Derivat passivierten pyrophoren Metalls als Füllung eines Fülldrahtes für die Behandlung von Metallschmelzen.Use of a 0.5 to 5% by weight of an organic nitrogen compound based on a pyrophoric metal passivated with an s-triazine and / or guanidine derivative as a filler wire for the treatment of molten metals. Verwendung eines Fülldrahtes, dessen Füllung neben dem passivierten pyrophoren Metall 0 bis 90 Gew.% an zusätzlichen Komponenten enthält, für den Zweck nach Anspruch 1.Use of a cored wire, the filling of which contains, in addition to the passivated pyrophoric metal, 0 to 90% by weight of additional components, for the purpose of claim 1. Verwendung eines Fülldrahtes, dessen Füllung aus einem Gemisch aus 49 Gew.% passiviertem pyrophorem Metall und 51 Gew.% Ferrosilicium, ggf. mit einem Gehalt an 0,5 bis 1,0 Gew.% Seltenerdmetall, besteht, für den Zweck nach Anspruch 1.Use of a cored wire, the filling of which consists of a mixture of 49% by weight of passivated pyrophoric metal and 51% by weight of ferrosilicon, possibly with a content of 0.5 to 1.0% by weight of rare earth metal, for the purpose according to claim 1 . Verwendung eines Fülldrahtes nach einem der Ansprüche 1 bis 3 zur Herstellung von Gußeisen mit Kugelgraphit und Gußeisen mit Vermikulargraphit.Use of a cored wire according to one of claims 1 to 3 for the production of cast iron with spheroidal graphite and cast iron with vermicular graphite. Verwendung eines Fülldrahtes nach einem der Ansprüche 1 bis 3 zur Entschwefelung von Roheisenschmelzen.Use of a cored wire according to one of claims 1 to 3 for the desulfurization of pig iron melts. Verwendung eines Fülldrahtes nach einem der vorhergehenden Ansprüche, wobei das pyrophore Metall Magnesium ist.Use of a cored wire according to any one of the preceding claims, wherein the pyrophoric metal is magnesium. Verwendung eines Fülldrahtes gemäß Anspruch 6 zum Magnesiumlegieren von Metallschmelzen.Use of a cored wire according to claim 6 for magnesium alloying of molten metals. Fülldraht zur Behandlung von Metallschmelzen, umfassend einen metallenen Mantel, welcher ein Füllmaterial für die Behandlung von Metallschmelzen umgibt, wobei das Füllmaterial ein mit 0,5 bis 5 Gew.% einer organischen Stickstoffverbindung auf Basis eines s-Triazin- und/oder Guanidin-Derivates passiviertes pyrophores Metall darstellt.Cored wire for the treatment of metal melts, comprising a metal sheath, which a Filling material for the treatment of molten metal surrounds, the filling material being a pyrophoric metal passivated with 0.5 to 5% by weight of an organic nitrogen compound based on an s-triazine and / or guanidine derivative. Fülldraht gemäß Anspruch 8, wobei das pyrophore Metall Magnesium ist.Cored wire according to claim 8, wherein the pyrophoric metal is magnesium.
EP92119560A 1991-11-21 1992-11-16 Cored wire containing a passivated pyrophoric metal and its application Expired - Lifetime EP0546351B1 (en)

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DE4138231A DE4138231C1 (en) 1991-11-21 1991-11-21
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EP (1) EP0546351B1 (en)
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JP5600639B2 (en) * 2011-04-28 2014-10-01 株式会社神戸製鋼所 Wire for REM addition
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DE102012013662A1 (en) * 2012-07-10 2014-01-16 Mechthilde Döring-Freißmuth Filled wire and process for the treatment of molten iron
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DE4138231C1 (en) 1992-10-22
EP0546351B1 (en) 1996-12-27
EP0546351A3 (en) 1993-12-29
DE59207767D1 (en) 1997-02-06
ATE146822T1 (en) 1997-01-15
TR26635A (en) 1995-03-15
US5264023A (en) 1993-11-23
JPH05222427A (en) 1993-08-31

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