EP2405025B1 - Method for manufacturing alloy blanks - Google Patents

Method for manufacturing alloy blanks Download PDF

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Publication number
EP2405025B1
EP2405025B1 EP20110168903 EP11168903A EP2405025B1 EP 2405025 B1 EP2405025 B1 EP 2405025B1 EP 20110168903 EP20110168903 EP 20110168903 EP 11168903 A EP11168903 A EP 11168903A EP 2405025 B1 EP2405025 B1 EP 2405025B1
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EP
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Prior art keywords
alloy
mixture
brick
brick mixture
water
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German (de)
French (fr)
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EP2405025A1 (en
Inventor
Daniel Thomy
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Mfg Metall- und Ferrolegierungsgesellschaft Mbh Hafner Blondin & Tidou
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Mfg Metall- und Ferrolegierungsgesellschaft Mbh Hafner Blondin & Tidou
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates

Definitions

  • the invention relates to a process for the production of alloy moldings for providing a molten metal in a smelting furnace with at least one alloying component or increasing its content in the molten metal, wherein a molding mixture using water containing at least one castable alloying element and a binder, and the molding mixture is filled into a casting mold and processed and demoulded into an alloy molding insertable into the furnace.
  • the production of such moldings is basically such that initially a molding mixture is formed, the proportions of alloying element, water, binder and an aggregate in the form of a supporting grain, such as sand, contains. Subsequently, this molding mixture is compacted into the alloy molding, be it in a stone molding press or in a vibrator ( WO 2005/118892 A1 ). For this to be possible, the molding mixture must have a viscoplastic or crumbly consistency.
  • the water used is such that it is just sufficient to cause binding of the binder and to achieve the required consistency.
  • the compression of the molding mixture is a complex operation and requires the presence of a suitable press.
  • the alloy moldings must be such a strength that they can be placed as bulk material in a furnace and go through the furnace largely undamaged.
  • Essential for the achievement of such strength is the grain structure of the molding mixture. Difficulties here are alloying elements which are present in dust form, for example filter dusts or cast iron dusts. Also not ideal are relatively coarse alloying elements, such as crushed scrap parts, metal chips or the like. Strength difficulties also occur when a carbon carrier is processed as the alloying element.
  • the invention has for its object to provide a method for the production of alloy moldings, which is inexpensive and can be used to produce alloy moldings using alloying elements in dust form or piece shape with sufficient strength.
  • This object is achieved in that in the production of the molding mixture at least as much water is added that the molding mixture isszer secured, and that at least as much binder is added that the alloy molding produced from the molding mixture after seven days at the latest setting time at 20 ° C has a strength of at least 4 N / mm 2 , preferably at least 5 N / mm 2 , and that the molding mixture is poured into a large mold whose interior is divided into individual molds, which are filled with the molding mixture in a casting process, and that it is a setting without application of external pressure and finally the resulting alloy molding is removed from the mold.
  • the basic idea of the invention is therefore not to compress the molding mixture, but to produce by casting by first a pourable molding mixture is created and then poured into a mold and allowed to set, the aforementioned setting time with the complete pouring of the molding mixture into the mold starts. It has been found that this method processes both dusty and lumpy alloying elements into an alloy molding of sufficient strength can be, without this requires the use of a press.
  • the method is inexpensive to carry out, and it is versatile, since it is suitable for alloying elements of various kinds and different grain sizes up to the piece size. In this case, in order to avoid cavities in the alloy molding or lack of filling of the mold so much water is added that the molding mixture in the mold isszer convincedd, especially self-leveling. Under the latter is the property to understand that adjusts a flat surface without further action, such as shaking or stripping on the open side of the molding mixture poured into the mold.
  • Suitable alloying elements are metals, including those from which the molten metal essentially consists, in particular iron, but also copper, zinc, chromium, manganese, nickel, molybdenum, titanium or vanadium.
  • the iron may also be in the form of iron alloys such as FeSi, FeMn, FeCr, FeNi, FeMo, FeTi or FeV.
  • Metal oxides and ores, such as FeO, Fe 2 O 3 , MnO are also suitable.
  • the alloying agent may also be a metallic silicon, for example in the form of SiC.
  • the inventive method but also for processing carbon carriers and / or unbound carbon as alloying element, such as graphite, coke breeze, petroleum coke, pitch coke, dust, etc. They can be used for carburizing the molten metal.
  • the alloying element can also be a mixture of at least two of the abovementioned alloy constituents or alloying elements.
  • the lower limit for the addition of water is determined by the property of pourability of the molding mixture. In general, then sufficient water is present to ensure setting of the molding, especially if - as known in the art - cement is used.
  • the strength of the alloy molding with the same binder content is the lower, the higher the water content, ie it is to seek a compromise between good pourability of the molding mixture on the one hand and the final strength of the alloy molding on the other hand.
  • a superplasticizer as is customarily used in the production of concrete, for example lingninsulfonates, melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, polycarboxylates or hydroxycarboxylic acids and their salts (see standard EN 934-2).
  • the proportion of the flow agent should be in the range of 0.01 to 0.5 Wt .-%, based on the weight of the molding mixture are.
  • a good processability results when the molding mixture is added so much water and optionally flow agent that the molding mixture a slump (measured according to the standard DIN EN 459-2, but without strokes) of at least 15 cm, preferably 19 cm and advantageously not more than 21 cm has.
  • a slump measured according to the standard DIN EN 459-2, but without strokes
  • the weight ratio of water to solid in the molding mixture should not exceed a value of 0.8.
  • Suitable binders are the binders generally used for building materials, in particular hydraulic binders such as cement. Since the binder for the inventively provided use of the alloy molding is an impurity, the proportion of the binder should not be much higher than necessary in order to achieve the strength provided according to the invention. It is therefore expedient if the highest possible possible cement is used, because then the binder content can be kept low. There is a connection to the quantity the water added to achieve pourability such that the higher the water content, the higher the amount of binder must be. In order to achieve a fast setting, a setting accelerator can be added to the cement, which accelerates the solidification and hardening process. The addition of binder should not exceed 40% by weight, based on the total molding mixture, but better not more than 20% by weight, but always provided that the abovementioned minimum strength is achieved.
  • a support grain is added to the molding mixture. It should have a maximum grain size of 1.5 cm. Preferably, sand should be used and the support grain should desirably be present at 5 to 40% by weight based on the total molding mixture.
  • the invention further provides that the molding mixture is vibrated in the mold and / or the free surface is smoothed.
  • a shaking is particularly recommended if the water content and, where appropriate, the content of superplasticizer are so low that there is a risk of the formation of voids or incomplete filling of the mold.
  • the surface should preferably be sprayed with water immediately after the casting process.
  • the Surface be provided with a moisture-impermeable or moisturizing Abbeckung.
  • the inventive method is suitable both for the use of an alloying element, which is present in small pieces, preferably with a mean extent of 0.5 to 5 cm, but also for such an alloying element, which is added in dust or powder form, in particular with a grain size less than 0.1 mm.
  • both forms of alloying elements can be combined with each other, preferably in a weight ratio of 20:80 to 80:20.
  • Casting molds whose internal volume corresponds to the predetermined shape of the alloy molding can be used for the method according to the invention. Instead, however, a trough-shaped large mold can be used, whose interior is divided into individual forms, the large mold is filled with the molding mixture in a single casting. In this case, the interior of the large mold can be subdivided by webs which project upwards into the individual molds. It is then possible to fill the individual molds with the molding mixture so that the resulting alloy moldings are separated from each other. Alternatively, the large mold can also be filled so high that the free surface of the molding mixture is above the webs, so a one-piece structure in the form of a large molding similar to a (reversed) chocolate bar is created.
  • this large blank is then broken into individual pieces in a crusher, which are the alloy moldings form.
  • a break beyond the breaking of the webs between the individual moldings can be made so that the individual moldings thus formed form irregularly shaped molded pieces.
  • the invention also relates to the use of this alloy molding by adding it to a metal melting furnace during the melting of metal, preferably into a cupola furnace, converter, blast furnace or induction furnace.
  • EMC80 is meant a SiC raw material containing 80% pure SiC, the remainder being unreacted free C and SiO 2 .
  • the special agent 1 specified in Example 3 is the binder marketed by HeidelbergCement Bauscher für Geotechnik GmbH & Co. KG under the name “CEM-ROCK 489", while the special agent 2 specified in Example 4 is also from Heidelberg Cement Building Materials for Geotechnik GmbH & Co. KG is under the name “CEM-ROCK MFG” sold binder.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mold Materials And Core Materials (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Legierungsformlingen, um eine Metallschmelze in einem Schmelzofen mit wenigstens einem Legierungsbestandteil zu versehen oder dessen Anteil in der Metallschmelze zu vergrößern, wobei eine Formlingsmischung unter Verwendung eines den wenigsten einen gießfähige Legierungsbestandteil enthaltenden oder daraus bestehenden Legierungselements, von Wasser und eines Bindemittels hergestellt und die Formlingsmischung in eine Gießform gefüllt und zu einem in den Schmelzofen einbringbaren Legierungsformling verarbeitet und entformt wird.The invention relates to a process for the production of alloy moldings for providing a molten metal in a smelting furnace with at least one alloying component or increasing its content in the molten metal, wherein a molding mixture using water containing at least one castable alloying element and a binder, and the molding mixture is filled into a casting mold and processed and demoulded into an alloy molding insertable into the furnace.

Im Stand der Technik ist es bekannt, die Zusammensetzung einer Metallschmelze in einem Schmelzofen durch Zugabe von Legierungsformlingen gezielt zu beeinflussen, die ein Legierungselement enthalten, in dem ein oder mehrere Legierungsbestandteile vorhanden sind, sei es elementar oder in Form einer chemischen Verbindung. Ein Beispiel hierfür ist die Aufsilizierung von Eisenschmelzen in Kupolöfen mit Hilfe von Legierungsformlingen, die als Legierungselement einen Siliziumträger wie SiC oder FeSi enthalten (vgl. DE 1 583 262 B , DE 26 38 117 B , DE 196 02 486 C1 , DE 199 17 008 A1 ). Ein weiteres Beispiel ist die Zugabe von Eisenmaterialien als Legierungselement mittels diese enthaltenden Legierungsformlingen (vgl. DE 44 16 699 A1 , DE 297 03 389 U1 , DE 1 143 837 B , DE 197 12 042 C1 , WO 2005/118892 A1 , DE 10 2005 062 036 A1 ) in Eisenschmelzen, wobei die Zugabe in erster Linie aus Recyclinggründen geschieht. Dies kann auch kombiniert werden mit der Zugabe von Silizium (vgl. EP 1 624 079 A1 ). Solche Legierungsformlinge können auch in Vertikalkammerreduktinsöfen verwendet werden (vgl. DD 139 601 C ) oder zur Kühlmittelbeschickung in Stahlkonvertern ( DE 25 01 636 A ).In the prior art it is known to deliberately influence the composition of a molten metal in a smelting furnace by adding alloy moldings containing an alloying element in which one or more alloying constituents are present, be it elemental or in the form of a chemical compound. An example of this is the Aufsilizierung of molten iron in cupola with the help of alloy moldings containing a silicon substrate such as SiC or FeSi as alloying element (see. DE 1 583 262 B . DE 26 38 117 B . DE 196 02 486 C1 . DE 199 17 008 A1 ). Another example is the addition of iron materials as alloying elements by means of alloy moldings containing them (see. DE 44 16 699 A1 . DE 297 03 389 U1 . DE 1 143 837 B . DE 197 12 042 C1 . WO 2005/118892 A1 . DE 10 2005 062 036 A1 ) in molten iron, with the addition occurring primarily for recycling reasons. This can also be combined with the addition of silicon (cf. EP 1 624 079 A1 ). Such alloy moldings can also be used in vertical chamber reductin furnaces (cf. DD 139 601 C ) or to the coolant charge in steel converters ( DE 25 01 636 A ).

Im Übrigen ist es seit langem bekannt, bestimmte Materialien zu brikettieren, beispielsweise zur Schlackenbildung in Schmelzöfen (vgl. DE 43 08 294 A ) und zur Deponierung (vgl. DE 42 07 265 A1 ).Incidentally, it has long been known to briquet certain materials, for example, for slag formation in melting furnaces (see. DE 43 08 294 A ) and for landfilling (cf. DE 42 07 265 A1 ).

Die Herstellung solcher Formlinge geschieht grundsätzlich derart, dass zunächst eine Formlingsmischung gebildet wird, die Anteile aus Legierungselement, Wasser, Bindemittel und einem Zuschlagstoff in Form eines Stützkorns, wie z.B. Sand, enthält. Anschließend wird diese Formlingsmischung zu dem Legierungsformling verdichtet, sei es in einer Steinformpresse oder sei es in einem Rüttler ( WO 2005/118892 A1 ). Damit dies möglich ist, muss die Formlingsmischung eine zähplastische oder krümelige Konsistenz haben. Das dabei verwendete Wasser ist so bemessen, dass es gerade ausreichend ist, ein Abbinden des Bindemittels zu bewirken und die erforderliche Konsistenz zu erreichen.The production of such moldings is basically such that initially a molding mixture is formed, the proportions of alloying element, water, binder and an aggregate in the form of a supporting grain, such as sand, contains. Subsequently, this molding mixture is compacted into the alloy molding, be it in a stone molding press or in a vibrator ( WO 2005/118892 A1 ). For this to be possible, the molding mixture must have a viscoplastic or crumbly consistency. The water used is such that it is just sufficient to cause binding of the binder and to achieve the required consistency.

Das Verpressen der Formlingsmischung ist ein aufwendiger Arbeitsvorgang und setzt das Vorhandensein einer geeigneten Presse voraus. Mit Hilfe der Presse und dem Abbindeprozess müssen die Legierungsformlinge eine solche Festigkeit erhalten, dass sie als Schüttgut in einen Schmelzofen aufgegeben werden können und den Schmelzofen weitgehend unbeschädigt durchlaufen. Wesentlich für die Erlangung einer solchen Festigkeit ist der Kornaufbau der Formlingsmischung. Schwierigkeiten machen hier Legierungselemente, die in Staubform vorliegen, beispielsweise Filterstäube oder Gießhallenstäube. Ebenfalls nicht ideal sind relativ grobe Legierungselemente, beispielsweise zerkleinerte Schrottteile, Metallspäne oder dergleichen. Festigkeitsschwierigkeiten treten ebenfalls auf, wenn als Legierungselement ein Kohlenstoffträger verarbeitet wird.The compression of the molding mixture is a complex operation and requires the presence of a suitable press. With the help of the press and the setting process The alloy moldings must be such a strength that they can be placed as bulk material in a furnace and go through the furnace largely undamaged. Essential for the achievement of such strength is the grain structure of the molding mixture. Difficulties here are alloying elements which are present in dust form, for example filter dusts or cast iron dusts. Also not ideal are relatively coarse alloying elements, such as crushed scrap parts, metal chips or the like. Strength difficulties also occur when a carbon carrier is processed as the alloying element.

In der US 6, 409, 964 B1 ist ein Verfahren zur Herstellung von Legierungsformlingen beschrieben, mit dem eine Formlingsmischung hergestellt wird, die unterschiedliche Wassergehalte hat. Bei dem höchsten Wassergehalt von ungefähr 20 Gew.-% wird eine fließfähige und damit gießfähige Formlingsmischung erhalten, die in Gießformen gegossen wird. Nähere Angaben zu der Fließfähigkeit werden nicht gemacht. Gleichwohl wird auch bei diesem Wassergehalt ein Vibrationsgießen für notwendig gehalten, um ein vollständiges Füllen der Form zu sichern und das Entstehen von Lunkern zu vermeiden.In the US Pat. No. 6,409,964 B1 For example, a process for the production of alloy moldings is described, with which a molding mixture is produced, which has different water contents. At the highest water content of about 20% by weight, a flowable and thus pourable molding mixture is obtained which is poured into molds. Details on the flowability are not made. However, a vibration casting is considered necessary for this water content to ensure complete filling of the mold and to avoid the formation of voids.

In der DE 39 40 327 C1 wird eine Formlingsmischung zur Herstellung von Legierungsformlingen in Rüttelpressen verdichtet, um eine ausreichende Händlingsfestigkeit zu erhalten. Über die Gieß- bzw. Fließfähigkeit der Formlingsmischung wird in diesem Dokument nichts gesagt. Entsprechendes gilt für die in der US 3,151,972 A und in der WO 2005/118892 A1 offenbarten Formlingsmischungen, wobei in dem letzteren Dokument nur von einem Verfüllen der Formlingsmischung in eine Form die Rede ist.In the DE 39 40 327 C1 For example, a molding mixture for producing alloy moldings is compacted in vibrating presses in order to obtain a satisfactory handling strength. Nothing is said about the pourability or flowability of the molding mixture in this document. The same applies to the in the US 3,151,972 A and in the WO 2005/118892 A1 disclosed molding mixtures, wherein in The latter document is only a filling of the molding mixture in a form is the speech.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Legierungsformlingen bereitzustellen, das kostengünstig ist und mit dem sich Legierungsformlinge unter Verwendung von Legierungselementen auch in Staubform oder Stückform mit ausreichender Festigkeit herstellen lassen.The invention has for its object to provide a method for the production of alloy moldings, which is inexpensive and can be used to produce alloy moldings using alloying elements in dust form or piece shape with sufficient strength.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, dass bei der Herstellung der Formlingsmischung mindestens so viel Wasser zugesetzt wird, dass die Formlingsmischung selbstzerlaufend ist, und dass mindestens so viel Bindemittel zugegeben wird, dass der aus der Formlingsmischung hergestellte Legierungsformling nach spätestens sieben Tagen Abbindezeit bei 20°C eine Festigkeit von wenigstens 4 N/mm2, vorzugsweise wenigstens 5 N/mm2, hat, und dass die Formlingsmischung in eine Großgießform eingegossen wird, deren Innenraum in Einzelformen unterteilt ist, die mit der Formlingsmischung in einem Gießvorgang gefüllt werden, und dass darin ein Abbinden ohne Anwendung äußerer Druckeinwirkung erfolgt und schließlich der so entstandene Legierungsformling entformt wird. Grundgedanke der Erfindung ist es folglich, die Formlingsmischung nicht zu verpressen, sondern mittels Gießen herzustellen, indem zunächst eine gießfähige Formlingsmischung erstellt wird und diese dann in eine Gießform gegossen und abbinden gelassen wird, wobei die vorerwähnte Abbindezeit mit dem vollständigen Eingießen der Formlingsmischung in die Gießform beginnt. Es hat sich herausgestellt, dass mit diesem Verfahren sowohl staubförmige als auch grobstückige Legierungselemente zu einem Legierungsformling ausreichender Festigkeit verarbeitet werden können, ohne dass es hierfür des Einsatzes einer Presse bedarf. Das Verfahren ist kostengünstig durchführbar, und es ist vielseitig einsetzbar, da es sich für Legierungselemente verschiedenster Art und unterschiedlichster Korngrößen bis hin zur Stückigkeit eignet. Dabei wird zwecks Vermeidung von Lunkern in dem Legierungsformling oder mangelnder Ausfüllung der Gießform so viel Wasser zugesetzt, dass die Formlingsmischung in der Gießform selbstzerlaufend, insbesondere selbstnivellierend ist. Unter letzterem ist die Eigenschaft zu verstehen, dass sich an der offenen Seite der in die Gießform eingegossenen Formlingsmischung eine ebene Oberfläche ohne weitere Maßnahmen, beispielsweise Rütteln oder Abstreifen, einstellt.This object is achieved in that in the production of the molding mixture at least as much water is added that the molding mixture is selbstzerlaufend, and that at least as much binder is added that the alloy molding produced from the molding mixture after seven days at the latest setting time at 20 ° C has a strength of at least 4 N / mm 2 , preferably at least 5 N / mm 2 , and that the molding mixture is poured into a large mold whose interior is divided into individual molds, which are filled with the molding mixture in a casting process, and that it is a setting without application of external pressure and finally the resulting alloy molding is removed from the mold. The basic idea of the invention is therefore not to compress the molding mixture, but to produce by casting by first a pourable molding mixture is created and then poured into a mold and allowed to set, the aforementioned setting time with the complete pouring of the molding mixture into the mold starts. It has been found that this method processes both dusty and lumpy alloying elements into an alloy molding of sufficient strength can be, without this requires the use of a press. The method is inexpensive to carry out, and it is versatile, since it is suitable for alloying elements of various kinds and different grain sizes up to the piece size. In this case, in order to avoid cavities in the alloy molding or lack of filling of the mold so much water is added that the molding mixture in the mold is selbstzerlaufend, especially self-leveling. Under the latter is the property to understand that adjusts a flat surface without further action, such as shaking or stripping on the open side of the molding mixture poured into the mold.

Als Legierungselement kommen Metalle, auch solche, aus denen die Metallschmelze im Wesentlichen besteht, insbesondere Eisen, aber auch Kupfer, Zink, Chrom, Mangan, Nickel, Molybden, Titan oder Vanadium in Frage. Das Eisen kann auch in Form von Eisenlegierungen wie FeSi, FeMn, FeCr, FeNi, FeMo, FeTi oder FeV vorliegen. Metalloxide und -erze, wie FeO, Fe2O3, MnO eignen sich gleichfalls. Das Legierungsmittel kann aber auch ein metallisches Silizium sein, beispielsweise in Form von SiC, sein. Darüber hinaus eignet sich das erfindungsgemäße Verfahren aber auch zur Verarbeitung von Kohlenstoffträgern und/oder ungebundenem Kohlenstoff als Legierungselement, beispielsweise Graphit, Koksgrus, Petrolkoks, Pechkoks, Dichtstaub etc. Sie können zum Aufkohlen der Metallschmelze verwendet werden. Schließlich kann das Legierungselement auch eine Mischung von zumindest zwei der vorgenannten Legierungsbestandteile bzw. Legierungselemente sein.Suitable alloying elements are metals, including those from which the molten metal essentially consists, in particular iron, but also copper, zinc, chromium, manganese, nickel, molybdenum, titanium or vanadium. The iron may also be in the form of iron alloys such as FeSi, FeMn, FeCr, FeNi, FeMo, FeTi or FeV. Metal oxides and ores, such as FeO, Fe 2 O 3 , MnO are also suitable. However, the alloying agent may also be a metallic silicon, for example in the form of SiC. In addition, the inventive method but also for processing carbon carriers and / or unbound carbon as alloying element, such as graphite, coke breeze, petroleum coke, pitch coke, dust, etc. They can be used for carburizing the molten metal. Finally, the alloying element can also be a mixture of at least two of the abovementioned alloy constituents or alloying elements.

Bei dem erfindungsgemäßen Verfahren wird die Untergrenze für den Wasserzusatz durch die Eigenschaft der Gießfähigkeit der Formlingsmischung bestimmt. Im Allgemeinen liegt dann ausreichend Wasser vor, um ein Abbinden des Formlings zu gewährleisten, insbesondere wenn hierfür - wie im Stand der Technik bekannt - Zement verwendet wird.In the method according to the invention, the lower limit for the addition of water is determined by the property of pourability of the molding mixture. In general, then sufficient water is present to ensure setting of the molding, especially if - as known in the art - cement is used.

Zu beachten ist jedoch der Umstand, dass die Festigkeit des Legierungsformlings bei gleichem Bindemittelanteil um so geringer wird, je höher der Wasseranteil ist, d.h. es ist ein Kompromiss zwischen guter Gießfähigkeit der Formlingsmischung einerseits und der Endfestigkeit des Legierungsformlings andererseits zu suchen. Hierfür hilfreich ist die Zugabe eines Fließmittels, wie es gewöhnlich bei der Herstellung von Beton zur Anwendung kommt, beispielsweise Lingninsulfonate, Melamin-Formaldehyd-Sulfonate, Naphtalin-Formaldehyd-Sulfonate, Polycarboxylate oder Hydroxycarbonsäuren und deren Salze (vgl. Norm EN 934-2). Der Anteil des Fließmittels sollte im Bereich von 0,01 bis 0,5 Gew.-%, bezogen auf das Gewicht der Formlingsmischung, liegen. Durch Verwendung des Fließmittels wird der Wasseranspruch zwecks Herstellung der Gießfähigkeit deutlich herabgesetzt mit der Folge, dass der Legierungsformling eine höhere Festigkeit erhält oder zum Erreichen der erfindungsgemäßen Mindestfestigkeit ein geringerer Bindemittelanteil notwendig ist.It should be noted, however, that the strength of the alloy molding with the same binder content is the lower, the higher the water content, ie it is to seek a compromise between good pourability of the molding mixture on the one hand and the final strength of the alloy molding on the other hand. Helpful for this is the addition of a superplasticizer, as is customarily used in the production of concrete, for example lingninsulfonates, melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, polycarboxylates or hydroxycarboxylic acids and their salts (see standard EN 934-2). , The proportion of the flow agent should be in the range of 0.01 to 0.5 Wt .-%, based on the weight of the molding mixture are. By using the flow agent, the water requirement for the production of the pourability is significantly reduced with the result that the alloy molding receives a higher strength or to achieve the minimum strength according to the invention, a lower binder content is necessary.

Eine gute Verarbeitbarkeit ergibt sich, wenn der Formlingsmischung so viel Wasser und gegebenenfalls Fließmittel zugesetzt wird, dass die Formlingsmischung ein Ausbreitmaß (gemessen entsprechend der Norm DIN EN 459-2, jedoch ohne Hubstöße) von wenigstens 15 cm, vorzugsweise 19 cm und zweckmäßigerweise nicht mehr als 21 cm hat. Bei Werten von 15 bis 18 cm Ausbreitmaß empfiehlt sich zwecks Vermeidung von Hohlräumen zwischen Gießform und Formlingsmischung sowie von Lunkern im Legierungsformling ein Rütteln der Formlingsmischung in der Gießform. Zweckmäßigerweise sollte das Gewichtsverhältnis Wasser zu Feststoff in der Formlingsmischung einen Wert von 0,8 nicht überschreiten.A good processability results when the molding mixture is added so much water and optionally flow agent that the molding mixture a slump (measured according to the standard DIN EN 459-2, but without strokes) of at least 15 cm, preferably 19 cm and advantageously not more than 21 cm has. For values of 15 to 18 cm slump size, it is recommended to shake the mixture of foundries in the casting mold in order to avoid voids between the casting mold and the molding mixture and voids in the alloy molding. Conveniently, the weight ratio of water to solid in the molding mixture should not exceed a value of 0.8.

Als Bindemittel kommen die im Allgemeinen für Baustoffe verwendeten Bindemittel in Frage, insbesondere hydraulische Bindemittel wie Zement. Da das Bindemittel für den erfindungsgemäß vorgesehenen Einsatz des Legierungsformlings einen Fremdstoff darstellt, sollte der Anteil des Bindemittels nicht sehr viel höher sein als erforderlich, um die erfindungsgemäß vorgesehene Festigkeit zu erreichen. Es ist deshalb zweckmäßig, wenn möglichst hochwertiger Zement verwendet wird, denn dann kann der Bindemittelanteil gering gehalten werden. Dabei besteht ein Zusammenhang zu der Menge des zwecks Erreichen der Gießfähigkeit zugesetzten Wassers dergestalt, dass die Menge des Bindemittels um so höher sein muss, je höher der Wassergehalt ist. Um ein schnelles Abbinden zu erreichen, kann dem Zement auch ein Abbindebeschleuniger zugesetzt werden, der den Erstarrungs- und Erhärtungsprozess beschleunigt. Der Zusatz von Bindemittel sollte 40 Gew.-%, bezogen auf die gesamte Formlingsmischung, nicht überschreiten, besser jedoch nicht höher als 20 Gew.-% liegen, immer jedoch vorausgesetzt, dass die oben genannte Mindestfestigkeit erreicht wird.Suitable binders are the binders generally used for building materials, in particular hydraulic binders such as cement. Since the binder for the inventively provided use of the alloy molding is an impurity, the proportion of the binder should not be much higher than necessary in order to achieve the strength provided according to the invention. It is therefore expedient if the highest possible possible cement is used, because then the binder content can be kept low. There is a connection to the quantity the water added to achieve pourability such that the higher the water content, the higher the amount of binder must be. In order to achieve a fast setting, a setting accelerator can be added to the cement, which accelerates the solidification and hardening process. The addition of binder should not exceed 40% by weight, based on the total molding mixture, but better not more than 20% by weight, but always provided that the abovementioned minimum strength is achieved.

Nach der Erfindung ist ferner vorgesehen, dass der Formlingsmischung ein Stützkorn zugegeben wird. Es sollte eine Körnung von maximal 1,5 cm haben. Vorzugsweise sollte Sand verwendet werden, und das Stützkorn sollte zweckmäßigerweise mit einem Gewichtsanteil von 5 bis 40%, bezogen auf die gesamte Formlingsmischung, vorhanden sein.According to the invention, it is further provided that a support grain is added to the molding mixture. It should have a maximum grain size of 1.5 cm. Preferably, sand should be used and the support grain should desirably be present at 5 to 40% by weight based on the total molding mixture.

Die Erfindung sieht des Weiteren vor, dass die Formlingsmischung in der Gießform gerüttelt und/oder deren freie Oberfläche glatt gestrichen wird. Eine Rüttelung empfiehlt sich insbesondere dann, wenn der Wassergehalt und gegebenenfalls der Gehalt an Fließmittel so gering sind, dass die Gefahr der Bildung von Lunkern oder nicht vollständiger Ausfüllung der Gießform besteht.The invention further provides that the molding mixture is vibrated in the mold and / or the free surface is smoothed. A shaking is particularly recommended if the water content and, where appropriate, the content of superplasticizer are so low that there is a risk of the formation of voids or incomplete filling of the mold.

Damit es im Bereich der freien Oberfläche der in der Gießform befindlichen Formlingsmischung nicht zu einem ungenügenden Abbinden oder zur Rissbildung kommt, sollte die Oberfläche vorzugsweise unmittelbar nach dem Gießvorgang mit Wasser besprüht werden. Alternativ oder in Kombination dazu kann die Oberfläche mit einer feuchtigkeitsundurchlässigen oder feuchtigkeitsspendenden Abbeckung versehen werden.In order to prevent insufficient setting or crack formation in the region of the free surface of the casting mixture in the casting mold, the surface should preferably be sprayed with water immediately after the casting process. Alternatively or in combination, the Surface be provided with a moisture-impermeable or moisturizing Abbeckung.

Das erfindungsgemäße Verfahren eignet sich sowohl für die Verwendung eines Legierungselementes, das in kleinstückiger Form, vorzugsweise mit einer mittleren Erstreckung von 0,5 bis 5 cm, vorliegt, aber auch für ein solches Legierungselement, das in Staub- oder Pulverform zugegeben wird, insbesondere mit einer Korngröße unter 0,1 mm. Dabei können beide Formen von Legierungselementen miteinander kombiniert werden, vorzugsweise in einem Gewichtsverhältnis von 20:80 bis 80:20.The inventive method is suitable both for the use of an alloying element, which is present in small pieces, preferably with a mean extent of 0.5 to 5 cm, but also for such an alloying element, which is added in dust or powder form, in particular with a grain size less than 0.1 mm. In this case, both forms of alloying elements can be combined with each other, preferably in a weight ratio of 20:80 to 80:20.

Für das erfindungsgemäße Verfahren können Gießformen verwendet werden, deren Innenvolumen der vorbestimmten Formgebung des Legierungsformlings entspricht. Statt dessen kann jedoch auch eine wannenförmige Großform eingesetzt werden, deren Innenraum in Einzelformen unterteilt ist, wobei die Großform mit der Formlingsmischung in einem einzige Gießvorgang gefüllt wird. Dabei kann der Innenraum der Großform durch von deren Boden hochstehende Stege in die Einzelformen unterteilt sein. Es besteht dann die Möglichkeit, die Einzelformen mit der Formlingsmischung so zu füllen, dass die so entstehenden Legierungsformlinge voneinander getrennt sind. Alternativ kann die Großform aber auch so hoch gefüllt werden, dass die freie Oberfläche der Formlingsmischung oberhalb der Stege liegt, also ein einstückiges Gebilde in Form eines Großformlings ähnlich einer (umgedrehten) Schokoladentafel entsteht. Nach dem Entformen wird dieser Großformling dann in einem Brecher in einzelne Stücke gebrochen, die die Legierungsformlinge bilden. Dabei kann auch ein Brechen über das Brechen der Stege zwischen den Einzelformlingen hinaus vorgenommen werden, so dass die so gebildeten Einzelformlinge unregelmäßig geformte Formlingsstücke bilden.Casting molds whose internal volume corresponds to the predetermined shape of the alloy molding can be used for the method according to the invention. Instead, however, a trough-shaped large mold can be used, whose interior is divided into individual forms, the large mold is filled with the molding mixture in a single casting. In this case, the interior of the large mold can be subdivided by webs which project upwards into the individual molds. It is then possible to fill the individual molds with the molding mixture so that the resulting alloy moldings are separated from each other. Alternatively, the large mold can also be filled so high that the free surface of the molding mixture is above the webs, so a one-piece structure in the form of a large molding similar to a (reversed) chocolate bar is created. After demoulding, this large blank is then broken into individual pieces in a crusher, which are the alloy moldings form. In this case, a break beyond the breaking of the webs between the individual moldings can be made so that the individual moldings thus formed form irregularly shaped molded pieces.

Gegenstand der Erfindung ist neben dem erfindungsgemäßen Verfahren auch die Verwendung dieses Legierungsformlings durch Zugabe in einen Metallschmelzofen beim Schmelzen von Metall, vorzugsweise in einen Kupolofen, Konverter, Hochofen oder Induktionsofen.In addition to the process according to the invention, the invention also relates to the use of this alloy molding by adding it to a metal melting furnace during the melting of metal, preferably into a cupola furnace, converter, blast furnace or induction furnace.

Nach dem erfindungsgemäßen Verfahren wurden beispielhaft folgende Legierungsformlinge hergestellt.The following alloy examples were prepared by the process according to the invention by way of example.

Beispiel 1example 1

SiC-Staub mit einer Körnung < 0,2 mmSiC dust with a grain size <0.2 mm 35,97 %35.97% ESiC80 mit einer Körnung von 0,1 - 10,0 mmESiC80 with a grain size of 0.1 - 10.0 mm -- Stützkorn mit einer Körnung von 0,5 - 1,0 cmSupport grain with a grain size of 0.5 - 1.0 cm 21,58 %21.58% Zement der Qualität CEM I 52,5 N (DIN EN 197-1)Cement grade CEM I 52.5 N (DIN EN 197-1) %% Fließmittel auf NaphtalinbasisNaphthalene-based superplasticizer -- Wasserwater 28,06 %28.06% Ausbreitmaßslump 16,4 cm16.4 cm Druckfestigkeit nach 7 Tagen bei 20°C'Compressive strength after 7 days at 20 ° C ' 5,4 N/mm2 5.4 N / mm 2

Beispiel 2Example 2

SiC-Staub mit einer Körnung < 0,2 mmSiC dust with a grain size <0.2 mm 32,85 %32.85% ESiC80 mit einer Körnung von 0,1 - 10,0 mmESiC80 with a grain size of 0.1 - 10.0 mm 25,55 %25.55% Stützkorn mit einer Körnung von 0,5 - 1,0 cmSupport grain with a grain size of 0.5 - 1.0 cm -- Zement der Qualität CEM I 52,5 N (DIN EN 197-1)Cement grade CEM I 52.5 N (DIN EN 197-1) 14,53 %14.53% Fließmittel auf NaphtalinbasisNaphthalene-based superplasticizer 0, 07 %0, 07% Wasserwater 27,01 %27.01% Ausbreitmaßslump 20,0 cm20.0 cm Druckfestigkeit nach 4 Tagen bei 20°C'Compressive strength after 4 days at 20 ° C ' 5,0 N/mm2 5.0 N / mm 2 Druckfestigkeit nach 7 Tagen bei 20°C'Compressive strength after 7 days at 20 ° C ' 6,4 N/mm2 6.4 N / mm 2

Beispiel 3Example 3

SiC-Staub mit einer Körnung < 0,2 mmSiC dust with a grain size <0.2 mm 32,61 %32.61% ESiC80 mit einer Körnung von 0,1 - 10,0 mmESiC80 with a grain size of 0.1 - 10.0 mm 25,36 %25.36% Stützkorn mit einer Körnung von 0,5 - 1,0 cmSupport grain with a grain size of 0.5 - 1.0 cm -- Sonderbindemittel 1Special binders 1 14,42 %14.42% Fließmittel auf NaphtalinbasisNaphthalene-based superplasticizer 0,07 %0.07% Wasserwater 27,54 %27.54% Ausbreitmaßslump 20,3 cm20.3 cm Druckfestigkeit nach 2 Tagen bei 20°C'Compressive strength after 2 days at 20 ° C ' 5,5 N/mm2 5.5 N / mm 2 Druckfestigkeit nach 7 Tagen bei 20°C'Compressive strength after 7 days at 20 ° C ' 7,5 N/mm2 7.5 N / mm 2

Beispiel 4Example 4

Unter "ESiC80" ist ein SiC-Rohstoff zu verstehen, der 80% reines SiC enthält, wobei der Rest nicht-reagiertes freies C und SiO2 ist. Bei dem im Beispiel 3 angegebenen Sondermittel 1 handelt es sich um das von der HeidelbergCement Baustoffe für Geotechnik GmbH & Co. KG unter dem Namen "CEM-ROCK 489" vertriebene Bindemittel, während das in Beispiel 4 angegebene Sondermittel 2 das ebenfalls von der Heidelberg Zement Baustoffe für Geotechnik GmbH & Co. KG unter der Bezeichnung "CEM-ROCK MFG" vertriebene Bindemittel ist.By "ESiC80" is meant a SiC raw material containing 80% pure SiC, the remainder being unreacted free C and SiO 2 . The special agent 1 specified in Example 3 is the binder marketed by HeidelbergCement Baustoffe für Geotechnik GmbH & Co. KG under the name "CEM-ROCK 489", while the special agent 2 specified in Example 4 is also from Heidelberg Cement Building Materials for Geotechnik GmbH & Co. KG is under the name "CEM-ROCK MFG" sold binder.

Claims (13)

  1. Method for producing alloy bricks in order to provide molten metal in a furnace with at least one alloy component or to increase the amount thereof in the molten metal wherein a castable brick mixture is made by using the alloy element comprising the at least one alloy component or consisting thereof, water and a binder and wherein the brick mixture is filled into a mould, transformed into an alloy brick introducible into the furnace and is demoulded, characterized in that during production at least such an amount of water is added to the brick mixture that the brick mixture is self-spreading, particularly self-levelling, and that at least such an amount of binder is added that the alloy brick made from the alloy mixture, after a setting time of seven days at 20°C at the latest, has reached a strength of at least 4 N/mm2, preferably at least 5 N/mm2, that the brick mixture is casted into a large mould, the interior thereof being divided into single moulds, which are filled with the brick mixture in a casting process, and that a setting takes place therein without applying external pressure.
  2. Method according to claim 1, characterized in that a metal, particularly iron, also as an iron alloy like FeSi, FeMn, FeCr, FeNi, FeMo, FeTi, FeV, and/or particularly Copper, Zinc, Chromium, Manganese, Nickel, Molybdenum, Titanium, Vanadium, or as metal oxide and ores, like FeO, Fe2O3, MnO, and/or SiC and/or a Carbon carrier and/or unbound Carbon, for instance graphite, coke breeze, petroleum coke, pitch coke, carburizing dust for carburizing the molten metal or a mixture of at least two of said alloy components is used.
  3. Method according to claim 1 or 2, characterized in that such an amount of water and possibly plasticizer is added to the brick mixture that it has a flow spread amount of at least 15 cm, preferably 19 cm and appropriately not more than 21 cm.
  4. Method according to one of claims 1 to 3, characterized in that a plasticizer and/or an accelerator is added to the brick mixture.
  5. Method according to one of claims 1 to 4, characterized in that the weight ratio water to solid material does not exceed a value of 0.8 and/or the plasticizer comprises a hydraulic binder, particularly cement, or consists thereof.
  6. Method according to one of claims 1 to 5, characterized in that the addition of binder does not exceed 40 weight-%, preferably 20 weight-% related to the brick mixture as a whole, and/or that support particles are added to the brick mixture, appropriately with a grain size of maximal 1.5 cm, wherein the support particles preferably are sand and particularly have a weight share of 5 to 40 %, related to the weight of the brick mixture as a whole.
  7. Method according to one of claims 1 to 6, characterized in that the brick mixture is vibrated in the mould and/or the free surface thereof is smoothed down.
  8. Method according one of claims 1 to 7, characterized in that the surface of the brick mixture in the mould is sprayed with water preferably immediately after the casting process.
  9. Method according to one of claims 1 to 8, characterized in that the surface of the brick mixture in the mould, possibly after spraying with water, is provided with a cover impermeable to humanity or a moisturizing cover.
  10. Method according to one of claims 1 to 9, characterized in that the alloy element for producing the brick mixture in small-sized form, is used preferably with a middle extension between 0.5 to 5 cm.
  11. Method according one of claims 1 to 10, characterized in that the alloy element is added in dust or powder form, particularly with a grain size below 0.1 mm.
  12. Method according to claim 10 or 11, characterized in that the at least one alloy element is used both in small-sized and in dust or powder form, and that the weight ratio of their components is between 20:80 and 80:20.
  13. Method according one of claims 1 to 12, characterized in that the large mould is divided into single moulds by upstanding webs and the brick mixture is filled in higher than the webs, and that the large brick made this way is broken into single small-sized alloy bricks after setting.
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