EP1919645B1 - Process for producing metal-containing castings, and associated apparatus - Google Patents

Process for producing metal-containing castings, and associated apparatus Download PDF

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Publication number
EP1919645B1
EP1919645B1 EP06778066A EP06778066A EP1919645B1 EP 1919645 B1 EP1919645 B1 EP 1919645B1 EP 06778066 A EP06778066 A EP 06778066A EP 06778066 A EP06778066 A EP 06778066A EP 1919645 B1 EP1919645 B1 EP 1919645B1
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EP
European Patent Office
Prior art keywords
melt
mold
metal
copper mould
voltage source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP06778066A
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German (de)
French (fr)
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EP1919645A1 (en
Inventor
Stefan Roth
Ludwig Schultz
Mihai Stoica
Andras Bardos
Lajos K. Varga
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Leibnitz-Institut fur Festkorper- und Werkstoffforschung Dresden Ev
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Leibnitz-Institut fur Festkorper- und Werkstoffforschung Dresden Ev
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/02—Use of electric or magnetic effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007—Semi-solid pressure die casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/30—Accessories for supplying molten metal, e.g. in rations
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys

Definitions

  • the invention relates to the fields of materials science and process engineering and relates to a method for the production of moldings from metallic glasses and an apparatus for implementing this method.
  • a metallic glass is a metastable alloy that has no long-range order, unlike normal crystalline materials. Its structure is amorphous and resembles that of a liquid. To obtain the amorphous state on cooling, several conditions must be satisfied. Thus, nucleation and seed growth must be suppressed to freeze the structure of the liquid. To realize this, the metallic melt must be cooled very quickly, for example by contact with the surface of a very good heat-conducting heat sink. The quality of the thermal contact and the thickness and thermal conductivity of the liquid layer determine the cooling rate.
  • a well-known and widespread method for casting metals and also massive metallic glasses is the casting into cold molds.
  • the melt is forced by different measures in the mold and solidifies there in the form prescribed by the mold.
  • the mold is made of good heat conducting material.
  • the casting process is very fast. First, the metal is melted in a crucible, and then the melt is forced by gas pressure or centrifugal force into the mold.
  • the surface of the mold In order to ensure a good thermal contact between the metallic melt and the mold, advantageously made of copper, the surface of the mold must be very clean. This can be easily realized by mechanical cleaning and pickling.
  • the melt should wet the mold well. The wetting depends essentially on the viscosity and interfacial tension of the melt with respect to the copper mold and with respect to the ambient atmosphere. The viscosity depends very much on the temperature. It decreases exponentially with increasing temperature, while the interfacial tensions decrease linearly with increasing temperature. Small values of viscosity and interfacial tension, which are desirable for good wetting and for good filling of the mold, can in principle be set by a high temperature.
  • the object of the present invention is to provide a method for producing cast articles on metallic glasses and a device therefor, in which in addition high cooling rates and a good mold filling during casting without overheating a metal-containing melt is achieved.
  • a good mold filling at high cooling rates is achieved without overheating the metal-containing melt.
  • the application of the electrical voltage between the metal-containing melt and the electrically conductive mold at least during the introduction into the mold the interfacial tension of the metal-containing melt is lowered. This leads to a good thermal contact between the metal-containing melt and the electrically conductive casting mold, whereby a more complete filling of the casting mold is achieved without overheating the metal-containing melt.
  • more complicated shaped parts for example made of solid metallic glasses, can be produced more easily and in larger dimensions.
  • the introduction of the metal-containing melt in the mold takes place in a closed system under Inert gas atmosphere.
  • the inductively molten metal-containing melt is pressed by overpressure of the atmosphere, such as argon atmosphere, into the mold.
  • the tension can be changed for each shaping operation or even during a shaping operation. In this case, a short-circuit current between metal-containing melt and electrically conductive mold is predetermined.
  • the main advantage of the solution according to the invention is the specific variability of the wetting behavior between the melt and the mold without overheating of the melt so that the melt wets the mold better and the contact between melt and mold becomes more homogeneous. Depending on the type of melt, specific property improvements result for different materials.
  • Another advantage of the solution according to the invention is that the coercive force of the produced castings is smaller and their magnetization is higher by the application of electrical voltage during the molding process in soft magnetic materials. This is achieved by lower internal stresses during shaping, which is due to the more homogeneous cooling and then leads to improved magnetic and mechanical properties of the product according to the invention. In addition, complex shapes are better formed and the products according to the invention also become mechanically stronger.
  • a metallic melt is produced in an induction furnace under argon atmosphere.
  • a tungsten electrode which is connected to a voltage source, reaches into the metallic melt.
  • the copper mold is also electrically connected to the voltage source. After applying the voltage of 230 V, the outflow opening in the induction furnace is opened. At the same time, an argon overpressure of 200 kPa is applied. As a result, the metallic melt is pressed into the recess in the copper mold and fills it completely due to the lower surface tension. After cooling and opening the copper mold is a complete annular disc with the desired dimensions.
  • the alloy Fe 65.5 Cr 4 Mo 4 Ga 4 P 12 C 5 B 5.5 can not be cast amorphously into an annular disc according to the methods of the prior art. According to the method of Example 1 can now be made of this alloy a complete annular disc, wherein the product is in an amorphous form.

Abstract

Method such as can be used, for example, for producing molded articles from metallic glasses. Method and apparatus are provided in which a good mold filling during casting is achieved in addition to high cooling rates. The method includes introducing a metal-containing melt into an electrically conducting casting mold, the metal-containing melt and the mold being connected in an electrically conducting manner to the outputs of the same voltage source during the introduction into a casting mold, so that a preset current flows through the boundary interface between the melt and the mold. Apparatus is also provided in which there is an electrically conducting connection to a voltage source between a metal-containing melt and an electrically conducting mold for the melt.

Description

Die Erfindung bezieht sich auf die Gebiete der Materialwissenschaften und der Verfahrenstechnik und betrifft ein Verfahren zur Herstellung von Formkörpern aus metallischen Gläsern und eine Vorrichtung zur Realisierung dieses Verfahrens.The invention relates to the fields of materials science and process engineering and relates to a method for the production of moldings from metallic glasses and an apparatus for implementing this method.

Ein metallisches Glas ist eine metastabile Legierung, die im Gegensatz zu normalen kristallinen Materialien keine Fernordnung aufweist. Seine Struktur ist amorph und ähnelt der einer Flüssigkeit. Um den amorphen Zustand beim Abkühlen zu erhalten, müssen mehrere Bedingungen erfüllt sein. So müssen die Keimbildung und das Keimwachstum unterdrückt werden, um die Struktur der Flüssigkeit einzufrieren. Um dies zu realisieren, muss die metallische Schmelze sehr schnell abgekühlt werden, beispielsweise durch Kontakt mit der Oberfläche eines sehr gut wärmeleitenden Kühlkörpers. Die Güte des Wärmekontaktes und Dicke und Wärmeleitfähigkeit der Flüssigkeitsschicht bestimmen die Abkühlrate.A metallic glass is a metastable alloy that has no long-range order, unlike normal crystalline materials. Its structure is amorphous and resembles that of a liquid. To obtain the amorphous state on cooling, several conditions must be satisfied. Thus, nucleation and seed growth must be suppressed to freeze the structure of the liquid. To realize this, the metallic melt must be cooled very quickly, for example by contact with the surface of a very good heat-conducting heat sink. The quality of the thermal contact and the thickness and thermal conductivity of the liquid layer determine the cooling rate.

Ein bekanntes und weit verbreitetes Verfahren, um Metalle und auch massive metallische Gläser zu gießen, ist der Abguss in kalte Kokillen. Dabei wird die Schmelze durch unterschiedliche Maßnahmen in die Kokille gezwungen und erstarrt dort in der durch die Kokille vorgegebenen Form.A well-known and widespread method for casting metals and also massive metallic glasses is the casting into cold molds. The melt is forced by different measures in the mold and solidifies there in the form prescribed by the mold.

Um im Falle von metallischen Gläsern hohe Abkühlraten zu erzielen, wird die Kokille aus gut wärmeleitendem Material hergestellt. Der Gießvorgang erfolgt dabei sehr schnell. Zunächst wird das Metall in einem Tiegel aufgeschmolzen, und anschließend wird die Schmelze durch Gasdruck oder Fliehkraft in die Form gezwungen.In order to achieve high cooling rates in the case of metallic glasses, the mold is made of good heat conducting material. The casting process is very fast. First, the metal is melted in a crucible, and then the melt is forced by gas pressure or centrifugal force into the mold.

Um einen guten Wärmekontakt zwischen der metallischen Schmelze und der Kokille, vorteilhafterweise aus Kupfer, zu gewährleisten, muss die Oberfläche der Form sehr sauber sein. Dies kann durch mechanisches Säubern und Beizen leicht realisiert werden. Außerdem sollte die Schmelze die Form gut benetzen. Die Benetzung hängt im Wesentlichen von der Viskosität und Grenzflächenspannung der Schmelze gegenüber der Kupferkokille und gegenüber der Umgebungsatmosphäre ab. Die Viskosität hängt sehr stark von der Temperatur ab. Sie nimmt exponentiell mit zunehmender Temperatur ab, während die Grenzflächenspannungen linear mit zunehmender Temperatur abnehmen. Kleine Werte von Viskosität und Grenzflächenspannung wie sie für eine gute Benetzung und für eine gute Füllung der Form anzustreben sind, können prinzipiell durch eine hohe Temperatur eingestellt werden. Allerdings bedingt eine Temperaturerhöhung auch eine höhere abzuführende Wärmemenge, was zu einer geringeren Abkühlgeschwindigkeit führt und deshalb nicht anzustreben ist. Ein Überhitzen der Schmelze führt beim Gießen kristalliner Legierungen zur guten Füllung der Form, aber beim Gießen metallischer Gläser ist die Überhitzung zu vermeiden, um den amorphen Zustand einfrieren zu können.In order to ensure a good thermal contact between the metallic melt and the mold, advantageously made of copper, the surface of the mold must be very clean. This can be easily realized by mechanical cleaning and pickling. In addition, the melt should wet the mold well. The wetting depends essentially on the viscosity and interfacial tension of the melt with respect to the copper mold and with respect to the ambient atmosphere. The viscosity depends very much on the temperature. It decreases exponentially with increasing temperature, while the interfacial tensions decrease linearly with increasing temperature. Small values of viscosity and interfacial tension, which are desirable for good wetting and for good filling of the mold, can in principle be set by a high temperature. However, a temperature increase also causes a higher amount of heat to be dissipated, which leads to a lower cooling rate and therefore is not desirable. Overheating of the melt during casting of crystalline alloys leads to good filling of the mold, but when casting metallic glasses, avoid overheating in order to freeze the amorphous state.

Es ist außerdem bekannt, dass Verunreinigungen der Schmelze mit Sauerstoff die Herstellbarkeit metallischer Gläser beeinträchtigt und deren Eigenschaften verschlechtert. Dieser Effekt wird durch heterogene Keimbildung an Oxidteilchen in der Schmelze erklärt. Eine Methode zur elektrochemischen Reinigung der Schmelze vor dem Abguss durch einen Stromfluss zwischen einer auf der Schmelze schwimmenden Schlacke und der Metallschmelze wurde von S. Bossuyt et al., Master. Sci. Eng. A 375-377 (2004) 240-243 beschrieben.It is also known that impurities of the melt with oxygen impairs the manufacturability of metallic glasses and deteriorates their properties. This effect is explained by heterogeneous nucleation of oxide particles in the melt. A method for electrochemical cleaning of the melt prior to casting by a current flow between a slag floating on the melt and the molten metal was S. Bossuyt et al., Master. Sci. Closely. A 375-377 (2004) 240-243 described.

Die Aufgabe der vorliegenden Erfindung besteht in der Angabe eines Verfahren zur Herstellung von Gusskörpern an metallischen Gläsern und einer Vorrichtung dafür, bei denen neben hohen Abkühlraten auch eine gute Formausfüllung beim Gießen ohne Überhitzen einer metallhaltigen Schmelze erreicht wird.The object of the present invention is to provide a method for producing cast articles on metallic glasses and a device therefor, in which in addition high cooling rates and a good mold filling during casting without overheating a metal-containing melt is achieved.

Die Aufgabe wird durch die in den Ansprüchen angegebenen Erfindungen gelöst. Weiterbildungen sind Gegenstand der Unteransprüche.The object is achieved by the inventions specified in the claims. Further developments are the subject of the dependent claims.

Durch das erfindungsgemäße Verfahren und die erfindungsgemäße Vorrichtung wird eine gute Formausfüllung bei hohen Abkühlraten erreicht, ohne die metallhaltige Schmelze zu überhitzen. Das Anlegen der elektrischen Spannung zwischen der metallhaltigen Schmelze und der elektrisch leitfähigen Gussform mindestens während der Einbringung in die Gussform wird die Grenzflächenspannung der metallhaltigen Schmelze erniedrigt. Dies führt zu einem guten thermischen Kontakt zwischen metallhaltiger Schmelze und der elektrisch leitfähigen Gussform, wodurch eine vollkommenere Füllung der Gussform erreicht wird, ohne die metallhaltige Schmelze zu überhitzen. Auch sind mit dem erfindungsgemäßen Verfahren und Vorrichtung kompliziertere Formteile beispielsweise aus massiven metallischen Gläsern leichter und in größeren Abmessungen herstellen.By means of the method according to the invention and the device according to the invention, a good mold filling at high cooling rates is achieved without overheating the metal-containing melt. The application of the electrical voltage between the metal-containing melt and the electrically conductive mold at least during the introduction into the mold, the interfacial tension of the metal-containing melt is lowered. This leads to a good thermal contact between the metal-containing melt and the electrically conductive casting mold, whereby a more complete filling of the casting mold is achieved without overheating the metal-containing melt. Also, with the method and apparatus according to the invention, more complicated shaped parts, for example made of solid metallic glasses, can be produced more easily and in larger dimensions.

Das Einbringen der metallhaltigen Schmelze in die Gussform erfolgt in einem geschlossenen System unter Intertgasatmosphäre. Die induktiv erschmolzene metallhaltige Schmelze wird durch Überdruck der Atmosphäre, beispielsweise Argonatmosphäre, in die Form gepresst.
Die Spannung kann je Formgebungsvorgang oder auch während eines Formgebungsvorganges verändert werden. Dabei ist ein Kurzschlussstrom zwischen metallhaltiger Schmelze und elektrisch leitender Gussform vorbestimmt.The introduction of the metal-containing melt in the mold takes place in a closed system under Inert gas atmosphere. The inductively molten metal-containing melt is pressed by overpressure of the atmosphere, such as argon atmosphere, into the mold.
The tension can be changed for each shaping operation or even during a shaping operation. In this case, a short-circuit current between metal-containing melt and electrically conductive mold is predetermined.

Hauptvorteil der erfindungsgemäßen Lösung ist die gezielte Veränderbarkeit des Benetzungsverhaltens zwischen Schmelze und Form ohne Überhitzung der Schmelze so, dass die Schmelze die Form besser benetzt und der Kontakt zwischen Schmelze und Form homogener wird. Je nach Art der Schmelze ergeben sich für verschiedene Werkstoffe spezifische Eigenschaftsverbesserungen.The main advantage of the solution according to the invention is the specific variability of the wetting behavior between the melt and the mold without overheating of the melt so that the melt wets the mold better and the contact between melt and mold becomes more homogeneous. Depending on the type of melt, specific property improvements result for different materials.

Ein weiterer Vorteil der erfindungsgemäßen Lösung besteht darin, dass durch das Anlage der elektrischen Spannung während des Formgebungsvorganges bei weichmagnetischen Werkstoffen die Koerzitivfeldstärke der hergestellten Gusskörper kleiner und deren Magnetisierung höher ist. Dies wird erreicht durch geringere innere Spannungen während der Formgebung, was auf die homogenere Abkühlung zurückzuführen ist und dann zu verbesserten magnetischen und mechanischen Eigenschaften des erfindungsgemäß hergestellten Produktes führt. Außerdem werden komplexe Formen besser ausgeformt und die erfindungsgemäß hergestellten Produkte auch werden mechanisch fester.Another advantage of the solution according to the invention is that the coercive force of the produced castings is smaller and their magnetization is higher by the application of electrical voltage during the molding process in soft magnetic materials. This is achieved by lower internal stresses during shaping, which is due to the more homogeneous cooling and then leads to improved magnetic and mechanical properties of the product according to the invention. In addition, complex shapes are better formed and the products according to the invention also become mechanically stronger.

Im Weiteren wird die Erfindung an mehreren Ausführungsbeispielen näher erläutert.Furthermore, the invention will be explained in more detail with reference to several embodiments.

Beispiel 1example 1

Aus 100 g einer FeCPBSiMn-Legierung (Gusseisen mit Bor- und Phosphorzusatz) wird in einem Induktionsofen unter Argonatmosphäre eine metallische Schmelze hergestellt. In die metallische Schmelze reicht eine Wolfram-Elektrode hinein, die mit einer Spannungsquelle verbunden ist. Unter dem Induktionsofen ist eine Kupferkokille angeordnet, die Aussparungen zur Ausformung einer gegossenen Ringscheibe enthält. Es soll eine Ringscheibe mit den Abmessungen, innerer Durchmesser = 18 mm, äußerer Durchmesser = 26 mm, Dicke = 1 mm, gegossen werden. Die Kupferkokille ist ebenfalls mit der Spannungsquelle elektrisch leitend verbunden. Nach Anlegen der Spannung von 230 V wird die Ausflussöffnung im Induktionsofen geöffnet. Gleichzeitig wird ein Argonüberdruck von 200 kPa angelegt. Dadurch wird die metallische Schmelze in die Aussparung in der Kupferkokille gedrückt und füllt diese aufgrund der geringeren Oberflächenspannung vollständig aus. Nach dem Abkühlen und Öffnen der Kupferkokille liegt eine vollständige Ringscheibe mit den gewünschten Abmessungen vor.From 100 g of a FeCPBSiMn alloy (cast iron with boron and phosphorus addition), a metallic melt is produced in an induction furnace under argon atmosphere. A tungsten electrode, which is connected to a voltage source, reaches into the metallic melt. Under the induction furnace, a copper mold is arranged, which contains recesses for molding a cast annular disc. It is an annular disk with the dimensions, inner diameter = 18 mm, outer diameter = 26 mm, thickness = 1 mm, poured become. The copper mold is also electrically connected to the voltage source. After applying the voltage of 230 V, the outflow opening in the induction furnace is opened. At the same time, an argon overpressure of 200 kPa is applied. As a result, the metallic melt is pressed into the recess in the copper mold and fills it completely due to the lower surface tension. After cooling and opening the copper mold is a complete annular disc with the desired dimensions.

Beispiel 2Example 2

Die Legierung Fe65,5Cr4Mo4Ga4P12C5B5,5 kann nach den Verfahren des Standes der Technik nicht amorph zu einer Ringscheibe gegossen werden. Gemäß dem Verfahren nach Beispiel 1 kann nun aus dieser Legierung eine vollständige Ringscheibe hergestellt werden, wobei das Produkt in amorpher Form vorliegt.The alloy Fe 65.5 Cr 4 Mo 4 Ga 4 P 12 C 5 B 5.5 can not be cast amorphously into an annular disc according to the methods of the prior art. According to the method of Example 1 can now be made of this alloy a complete annular disc, wherein the product is in an amorphous form.

Claims (6)

  1. Process for producing castings from metallic glasses, in which a metal-containing melt is melted in an induction furnace and this melt is introduced in a closed system with superatmospheric pressure of the inert gas atmosphere into a copper mould arranged thereunder, after application of a voltage between an electrode protruding into the melt and the copper mould the outflow opening in the induction furnace is opened and the melt is transferred into the copper mould by applying the superatmospheric pressure, so that a preset current flows through the boundary layer between the melt and the copper mould.
  2. Process according to Claim 1, in which over 50% by mass of the metal-containing melt is a metal.
  3. Process according to Claim 1, in which melted amorphous metals are used as the metal-containing melt.
  4. Process according to Claim 1, in which a voltage of from 0.5 V to 42 V is tapped at the voltage source.
  5. Apparatus for producing castings from metallic glasses, comprising an induction furnace with an outflow opening, a copper mould arranged thereunder, an electrode in the induction furnace, and a voltage source, which is connected in an electrically conducting manner to the electrode and the copper mould.
  6. Apparatus according to Claim 5, in which the metal-containing melt is connected to a voltage source by way of a tungsten electrode.
EP06778066A 2005-08-02 2006-07-28 Process for producing metal-containing castings, and associated apparatus Not-in-force EP1919645B1 (en)

Applications Claiming Priority (2)

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DE102005037982A DE102005037982B3 (en) 2005-08-02 2005-08-02 Process for producing metal-containing castings and apparatus therefor
PCT/EP2006/064809 WO2007014916A1 (en) 2005-08-02 2006-07-28 Process for producing metal-containing castings, and associated apparatus

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EP1919645A1 EP1919645A1 (en) 2008-05-14
EP1919645B1 true EP1919645B1 (en) 2010-04-21

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EP (1) EP1919645B1 (en)
JP (1) JP2009502515A (en)
KR (1) KR20080036624A (en)
CN (1) CN101237951A (en)
AT (1) ATE464963T1 (en)
DE (2) DE102005037982B3 (en)
WO (1) WO2007014916A1 (en)

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DE102011050149A1 (en) * 2010-11-17 2012-05-24 Ferrofacta Gmbh Die casting nozzle and die casting process
CN102974807A (en) * 2012-08-01 2013-03-20 南昌大学 Method and device for improving liquid metal mold-filling capacity
US9802247B1 (en) 2013-02-15 2017-10-31 Materion Corporation Systems and methods for counter gravity casting for bulk amorphous alloys
US10201638B2 (en) 2013-03-14 2019-02-12 Endologix, Inc. Systems and methods for forming materials in situ within a medical device
US10668529B1 (en) 2014-12-16 2020-06-02 Materion Corporation Systems and methods for processing bulk metallic glass articles using near net shape casting and thermoplastic forming

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CN101237951A (en) 2008-08-06
ATE464963T1 (en) 2010-05-15
JP2009502515A (en) 2009-01-29
EP1919645A1 (en) 2008-05-14
US8002014B2 (en) 2011-08-23
WO2007014916A1 (en) 2007-02-08
DE502006006811D1 (en) 2010-06-02
KR20080036624A (en) 2008-04-28
US20080295991A1 (en) 2008-12-04
DE102005037982B3 (en) 2007-03-15

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