EP0280765B1 - Procédé et installation pour la fabrication de pièces coulée de bains métallique d'alliages d'acier traité sous pression - Google Patents

Procédé et installation pour la fabrication de pièces coulée de bains métallique d'alliages d'acier traité sous pression Download PDF

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Publication number
EP0280765B1
EP0280765B1 EP87114822A EP87114822A EP0280765B1 EP 0280765 B1 EP0280765 B1 EP 0280765B1 EP 87114822 A EP87114822 A EP 87114822A EP 87114822 A EP87114822 A EP 87114822A EP 0280765 B1 EP0280765 B1 EP 0280765B1
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EP
European Patent Office
Prior art keywords
melt
pressure
casting
treatment vessel
vessel
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EP87114822A
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German (de)
English (en)
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EP0280765A2 (fr
EP0280765A3 (en
Inventor
Wolfgang Dipl.-Ing. Dr. Holzgruber
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Inteco Internationale Techinsche Beratung GmbH
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Inteco Internationale Techinsche Beratung GmbH
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/09Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting by using pressure
    • B22D27/13Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting by using pressure making use of gas pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00Treatment of fused masses in the ladle or the supply runners before casting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10Supplying or treating molten metal
    • B22D11/11Treating the molten metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10Supplying or treating molten metal
    • B22D11/11Treating the molten metal
    • B22D11/113Treating the molten metal by vacuum treating
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0081Treating and handling under pressure

Definitions

  • the invention relates to a process for the production of castings, such as blocks, strands or molded parts made of metals, in particular of steels and steel-like alloys, which have higher contents of elements with high vapor pressure or gases than in the molten state at atmospheric pressure and remain in solution during solidification , and a device according to the preambles of claims 7, 8 and 11.
  • Examples of this are the treatment of molten steel with alkaline earth metals, in particular with Ca, which usually has only a very limited solubility and has a vapor pressure of over 1 bar at the temperatures of the molten steel.
  • Another example is nitrogen, which is also only soluble to a limited extent, depending on the alloy composition.
  • Treatment of the liquid melt under excess pressure with alkaline earth metals, in particular with Ca, allows, for example, the conversion of the phosphorus from the metal into the slag under reducing conditions. Such a treatment also enables the deposition of Cu, Sn etc. and their transfer into the slag.
  • N represents the nitrogen content in the melt in percent by weight
  • K represents a proportionality constant, the size of which is determined, among other things, by the alloy composition
  • P the partial pressure of the nitrogen in bar.
  • the element nitrogen is an interesting alloying element in that it is able to stabilize austenite as a structural component in iron alloys and to increase its strength. Therefore, efforts are often made to set higher nitrogen contents in iron-based alloys than the solubility at atmospheric pressure.
  • melt induction melting In pressure induction melting, a conventional induction furnace is installed in a pressure chamber and the melt is produced under a pressure that is Setting the desired nitrogen content in the melt allows. The melt is then poured off under pressure and also allowed to solidify under pressure in the same pressure chamber. This procedure is common in laboratory systems and has been carried out several times for melt sizes up to 100 kg.
  • the metal is melted by a plasma arc in a melting vessel, nitrogen being added to the gas of the plasma torch. Since the nitrogen in the plasma is converted into the monatomic form, the solubility in the melt is increased at the same pressure, since this becomes directly proportional to the partial pressure of the nitrogen in the gas.
  • the plasma gas In order to avoid pore formation by N2 during the subsequent solidification of the melt - where the square root law is valid again - depending on the pressure, the plasma gas must also contain argon in addition to nitrogen in order to limit the nitrogen contents in the melt accordingly. To date, such a plant has been announced in the Soviet Union, which produces blocks up to about 1 t in weight.
  • a device of the type described in the introduction can be found in DE-A-32 32 551, which describes a brick ladle for casting steel, from which the steel is drawn off by a slide closure.
  • the invention is based on the object, while avoiding the disadvantages described above, to bring any metal melt produced under excess pressure in a targeted manner to desired levels of elements with high vapor pressure or gases that are above solubility at atmospheric pressure and then to bring them into pour off any mold and also let it solidify under pressure.
  • any pre-melt produced by any open melting unit is first poured under atmospheric pressure into a - refractory - heated treatment vessel, then a gas pressure above atmospheric pressure is built up over the melt and maintained throughout the heating and treatment time - -
  • the melt can be covered by a slag -, the melt is continuously stirred and / or flushed with gas and either by flushing with the elements or substances in the gaseous state and / or by adding alloys containing the element or the substance to the desired content of this element or substance, the gas pressure above the melt being at least that with the desired content of the melt in Equilibrium partial pressure of the corresponding element or substance corresponds, and that the melt after adjusting the composition and the casting temperature directly from the treatment vessel via a closable and openable closure and pouring element in a likewise under pressure - conventional - mold, ceramic or metallic mold or continuous casting mold is poured.
  • the melt is instead pressed directly into a casting mold by increasing the pressure above the melt by the - known per se - method of die casting.
  • the cast body thus formed is allowed to solidify, the pressure above the mold being maintained throughout the solidification phase; according to the invention, the pressure is kept or set as high as it corresponds to the vapor pressure of the element or substance alloyed under pressure in the melt during the transition from the liquid to the solid state.
  • a device according to the invention has a conventional ladle as a container, which is placed in a closable pressure tank.
  • the pressure vessel itself also forms the treatment vessel and is delivered fireproof.
  • Gas purging in the treatment vessel is expediently carried out using a gas purging plug, but in principle a purging plug can also be used. Stirring of the melt is generally effected by gas purging, but inductive stirring is also possible.
  • the melt can be heated inductively in the closed treatment vessel. Heating by means of a plasma torch or electric arc is also possible.
  • the alloying of the melt with the substances which are only soluble to a greater extent under pressure can be carried out in the case of gases such as nitrogen by flushing the melt with this gas.
  • gases such as nitrogen
  • the casting of the melt treated in the treatment vessel and brought to temperature can in principle be carried out in various ways, which will be described in more detail below.
  • a melt 10 is provided in a pressure vessel 12 closed by a lid 11 in a conventional ladle 13, which is opened by opening a slide closure 15 engaging under a melt outlet 14 into a one under the ladle 13 - in turn in the pressure vessel 12 - Mold or mold 16, is poured.
  • the ladle 13 is closed by a pan lid 17 serving as radiation protection.
  • the melt 10 located in the ladle 13 is covered by a slag bath 20.
  • the latter is heated in this example according to the principle of electroslag heating by means of an immersed electrode 22, which is moved via a current-carrying electrode rod 24 in the interior 25 of the ladle 13 through a bushing 23.
  • the current is returned from the melt 10 via a counter electrode 26 in the wall 27 of the ladle 13 to a flange 28 of the pressure vessel 12 and from there via a line 29 to a current source 30.
  • the ladle 13 has a gas purging plug 32 and that melt outlet 14 with slide closure 15. Below the ladle 13, the mold 16 is arranged, into which the melt 10 is also poured off under pressure after the treatment has been completed. A pressure supply and discharge line 34 is installed in the cover 11.
  • a bricked-up treatment vessel 18 closed with a vessel lid 19 receives the melt 10 covered by the slag bath 20. Heating takes place in the manner already described via an electrode 22 immersed in the slag bath 20, which is moved in the treatment vessel 18 by means of the current-carrying electrode rod 24 passing through the pressure feedthrough 23.
  • a slide closure 15 is used as the casting device, which is installed in a slide chamber 40, which is likewise under pressure and can be closed with a closure member 36.
  • a flange 37 adjoins the closure member 36 and can be pressure-tightly connected to a counter flange 38 on the container lid 42 of a container 44 of a casting chamber 46.
  • a closure member 41 is installed between the counter flange 38 and the container lid 42, with the aid of which the casting chamber 46 can be closed in a pressure-tight manner.
  • the interior 25 of the treatment vessel 18, the slide chamber 40 and the casting chamber 46 are connected to a pressure supply and discharge line 34 - which also serves as a pressure compensation line.
  • a casting mold 16 is placed in the casting chamber 46, and the flanges 37, 38 of the casting chamber 46 and slide chamber 40 are connected in a pressure-tight manner, the closure member 41 remaining open.
  • the casting chamber 46 is then brought to the same pressure that prevails in the treatment vessel 18.
  • the closure member 36 under the slide chamber 40 can now be opened.
  • the system is now ready for casting.
  • the casting process is initiated by opening the slide closure 15.
  • the melt 10 is solidified under pressure.
  • the closure member 41 installed below the connecting flange 38 to the slide chamber 40 can be closed. It is then possible to release the pressure from the treatment vessel 18 and the slide chamber 40 attached to it, to release the connection of the flanges 37, 38 between the slide chamber 40 and the casting chamber 46, and either to remove the latter with the casting or to remove the treatment vessel 18 and this in to prepare for a new treatment.
  • siphon tube 50 Another possibility is pouring through a siphon tube 50, the melt 10 being pressed through the siphon tube 50, preferably by an overpressure in the treatment vessel 18.
  • 3 shows the bricked-up treatment vessel 18 with the melt 10.
  • the siphon tube 50 - starting from the lowest point in the vessel bottom 48 - is provided, which can be locked by a closure member 36.
  • the flange 37 for the connection to the counter flange 38 is again attached to the cover 42 of the casting chamber 46 described above. Connecting and separating the casting chamber 46 and siphon tube 50 is carried out in the manner described above.
  • the casting is carried out by increasing the pressure in the treatment vessel 18.
  • the outlet of the siphon tube 50 is kept closed by that closure member 36. If a higher pressure is maintained in the siphon tube 50 than above the melt 10 in the treatment vessel 18, the melt 10 can be pushed back to the bottom and freezing in the unheated siphon tube 50 can be avoided. Alternatively, it is also possible to keep the siphon tube 50 inductively warm.
  • the flange connection 37, 38 is closed again and, with the closure member 41 open, the pressure in the casting chamber 46 is built up until it corresponds to that in the siphon tube 50.
  • the closure member 36 can be opened - the system is ready to pour.
  • the casting is now initiated by increasing the pressure above the melt 10 in the treatment vessel 18.
  • the melt 10 is pushed up in the siphon tube 50 projecting laterally upwards until it reaches an edge at 52 at which the siphon tube 50 is guided downwards again at a distance from the bottom 48 of the vessel; the melt 10 runs over the edge 52 into the mold 16 below.
  • the pressure in the treatment vessel 18 is continuously increased until the mold 16 is filled.
  • shut-off device 36 is closed and - provided there is still melt 10 in the treatment vessel 18 - the pressure in the siphon tube 50 is increased in order to push the melt 10 back again.
  • the flange connection 37, 38 between the siphon tube 50 and the casting chamber 46 can be opened, the latter can be exchanged with a casting for a new casting chamber 46, and again - as described above - connected for a named casting process. If the melt 10 is consumed, only the closure member 41 is closed after the casting, and the treatment vessel 18 and the siphon tube 50 are relieved of pressure.
  • the flange connection 37, 38 can then be released, which makes it possible to prepare the treatment vessel 18 for the reception of a new melt 10.
  • a slide closure can also be attached to the side of the treatment vessel 18, which is again housed in its own slide chamber 40 e, which is closed with a closure member and can be pressurized.
  • An arrangement of this type for the continuous casting of pressure-treated melts is shown in FIG. 4.
  • the slide chamber 40 e can be closed again with a closure member 36, to which a flange 37 connects, which can be closed in a pressure-tight manner with the counter flange 38 of the horizontally arranged casting chamber 46 e of a horizontal container 44 e .
  • the horizontal continuous casting mold 16 e can be moved up to the slide closure 15 and flanged when the closure member 36 is open.
  • the dissolving power for gases generally decreases, it may be expedient to further increase the pressure in the casting chamber 46, 46 e immediately after the casting process until at least the corresponding one Equilibrium pressure is reached, which ensures pore- and bubble-free solidification.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Continuous Casting (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)

Claims (15)

  1. Procédé de fabrication de corps moulés, tels que des lingots, des barres ou des pièces coulées en moule, en des métaux, notamment des aciers et des alliages similaires à l'acier, qui présentent des teneurs plus élevées en éléments à pression de vapeur élevée ou en gaz qu'il n'en reste en solution à l'état liquide de fusion sous pression atmosphérique et lors de la solidification,
    caractérisé
    en ce qu'un bain fondu (10) produit dans un appareil de fusion ouvert est tout d'abord coulé sous pression atmosphérique dans un récipient de traitement (13, 18) pouvant être chauffé, en ce qu'on établit ensuite, au-dessus du bain fondu (10), une pression de gaz d'un niveau supérieur à la pression atmosphérique que l'on maintient tout au long du temps de chauffage et de traitement, en ce que le bain fondu (10) est continuellement brassé et/ou traversé par un gaz, et amené, ou par passage des éléments ou substances se trouvant à l'état gazeux et/ou par addition d'alliages renfermant l'élément ou la substance, à la teneur souhaitée en cet élément ou en cette substance, la pression de gaz au-dessus du bain fondu (10) correspondant au moins à la pression partielle de l'élément ou de la substance considéré(e) en équilibre avec la teneur souhaitée du bain fondu, et en ce que le bain fondu, après réglage de la composition et de la température de coulée, est directement coulé du récipient de traitement (13, 18), par l'intermédiaire d'un élément de fermeture et de coulée (15) pouvant être fermé et ouvert, dans une lingotière (16), un moule céramique ou métallique ou une lingotière de coulée continue (16e) se trouvant également sous pression, ou bien en ce que le bain fondu (10) est directement refoulé sous pression, par augmentation de la pression au-dessus du bain fondu, dans un moule de coulée, selon le principe de la coulée sous pression, le corps moulé ainsi formé étant ensuite soumis à la solidification.
  2. Procédé selon la revendication 1, caractérisé en ce que le bain fondu est recouvert par du laitier pendant toute la durée du chauffage et du traitement, et/ou en ce que la pression au-dessus du moule de coulée (16) est maintenue pendant toute la durée de la phase de solidification.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que, comme élément sous forme gazeuse avec lequel on allie le bain fondu, on introduit de l'azote, et/ou en ce que les éléments se trouvant à l'état gazeux à la température de fusion et sous la pression atmosphérique, sont constitués par un ou plusieurs élément(s) du groupe 2 ou 2a de la classification périodique.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le gaz produisant la pression, est de l'azote ou de l'argon.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'au cours de la solidification, la pression de gaz au-dessus du corps moulé est augmentée jusqu'à un niveau tel qu'on empêche la formation de piqûres ou de soufflures de gaz occasionnée par un saut systématique de solubilité au cours de la solidification.
  6. Procédé selon au moins l'une des revendications 1 à 5, caractérisé en ce que le chauffage du bain fondu (10) dans le récipient de traitement (13, 18) est effectué par induction, ou à l'aide d'une torche au plasma, ou par un arc électrique par l'intermédiaire d'une ou de plusieurs électrodes en graphite, ou bien au moyen d'au moins une électrode (22) consommable ou non consommable plongée dans un laitier électriquement conducteur selon le procédé de chauffage sous laitier électrique.
  7. Dispositif comportant au moins un récipient à garnissage intérieur réfractaire pourvu d'une ouverture (14) d'écoulement du bain fondu équipée d'une fermeture, notamment d'une fermeture à tiroir (15), ainsi que d'une entrée de gaz (brique pour insufflation de gaz 32), ce récipient étant destiné à un bain fondu (10) susceptible d'y être chauffé, notamment en vue de la mise en oeuvre du procédé selon au moins l'une des revendications 1 à 6, caractérisé en ce que le récipient est conçu sous la forme d'une poche de coulée (13) pouvant être chauffée, et est disposé dans un réservoir sous pression (12), au-dessus d'un moule de coulée (16) également logé dans le réservoir sous pression et recevant le bain fondu (10) venant de la poche de coulée (13).
  8. Dispositif comportant au moins un récipient avec garnissage intérieur réfractaire pourvu d'une ouverture (14) d'écoulement du bain fondu équipée d'une fermeture, notamment d'une fermeture à tiroir (15), ainsi que d'une entrée de gaz (brique pour insuflation de gaz 32), ce récipient étant destiné à un bain fondu (10) susceptible d'y être chauffé, notamment en vue de la mise en oeuvre du procédé selon au moins l'une des revendications 1 à 6, caractérisé en ce que le récipient est conçu sous la forme d'un récipient de traitement (18) pouvant être chauffé et obturé de manière étanche à la pression au moyen d'un couvercle (19), et son ouverture (14) d'écoulement du bain fondu est équipée d'au moins un organe de fermeture (36) étanche à la pression et d'un élément de raccordement (bride 37) associé à un élément conjugué (contre-bride 38), ce dernier étant monté sur un réservoir (44) pouvant être obturé de manière étanche à la pression et destiné à loger un moule de coulée (16) recevant le bain fondu (10) venant du récipient de traitement (18), l'élément conjugué (contre-bride 38) étant de préférence disposé avec un organe de fermeture (41) sur le couvercle (42) du réservoir (44) qui délimite une chambre de coulée (46).
  9. Dispositif selon la revendication 8, caractérisé en ce qu'entre le récipient de traitement (18) et l'organe de fermeture (36) étanche à la pression, est disposé un tube formant siphon (50) dirigé de manière inclinée vers le haut à partir de la partie la plus basse du fond (48) du récipient et conçu de manière à pouvoir se raccorder à la chambre de coulée sous pression (46).
  10. Dispositif selon la revendication 8 ou 9, caractérisé en ce que le tube formant siphon (50) est, à distance du fond (48) du récipient, à nouveau dirigé vers le bas, présente, sensiblement au niveau d'une bride de pression du couvercle (19) du récipient, une arête (52) formée par le changement de direction, et se transforme à partir de celle-ci en une extrémité sensiblement verticale.
  11. Dispositif comportant au moins un récipient avec garnissage intérieur réfractaire pourvu d'une ouverture (14) d'écoulement du bain fondu équipée d'une fermeture, notamment d'une fermeture à tiroir (15), ainsi que d'une entrée de gaz (brique pour insufflationn de gaz 32), ce récipient étant destiné à un bain fondu (10) susceptible d'y être chauffé, notamment en vue de la mise en oeuvre du procédé selon l'une des revendications 1 à 6, caractérisé en ce que le récipient est conçu sous la forme d'un récipient de traitement (18) pouvant être chauffé et obturé de manière étanche à la pression au moyen d'un couvercle (19), et son ouverture (14) d'écoulement du bain fondu est équipée d'au moins un organe de fermeture (36) étanche à la pression et d'un élément de raccordement (bride 37) associé à un élément conjugué (contre-bride 38), ce dernier étant monté sur un compartiment de coulée (44e) sensiblement horizontal destiné à loger une lingotière (16e) orientée de manière correspondante et recevant le bain fondu (10) venant du récipient de traitement (18).
  12. Dispositif selon l'une des revendications 8 à 11, caractérisé en ce que, sur le récipient de traitement (18), un organe de fermeture (36) étanche à la pression conçu comme élément de raccordement est associé à l'ouverture (14) d'écoulement du bain fondu, et, le cas échéant, une chambre de tiroir (40) est montée entre l'organe de fermeture (36) étanche à la pression et la fermeture (15) du récipient de traitement (18).
  13. Dispositif selon au moins l'une des revendications 8 à 12, caractérisé en ce que l'ouverture (14) d'écoulement du bain fondu du récipient de traitement (18), obturée par un organe de fermeture (15), est disposée latéralement sur le récipient de traitement (18) en son point le plus bas avec la chambre de tiroir (40e), l'organe de fermeture (36) et la bride (37) destinée au raccordement à la chambre de coulée (46e).
  14. Dispositif selon au moins l'une des revendications 8 à 13, caractérisé en ce que la chambre de coulée (46, 46e) destinée à loger la lingotière, le moule de coulée (16) ou une installation de coulée continue pour la coulée sous pression, comporte un contre-bride (38) destinée à être raccordée d'une manière étanche à la pression à la bride (37) de la chambre sous pression du récipient de traitement (18), un organe de fermeture (41) étanche à la pression étant raccordé, le cas échéant, à la bride (38).
  15. Dispositif selon au moins l'une des revendications 7 à 14, caractérisé en ce que la chambre de coulée (46, 46e), éventuellement refroidie par eau, est reliée par une conduite d'équilibrage de la pression (34), à la chambre de traitement (13, 18) et/ou à la chambre de tiroir (40).
EP87114822A 1987-03-03 1987-10-10 Procédé et installation pour la fabrication de pièces coulée de bains métallique d'alliages d'acier traité sous pression Expired - Lifetime EP0280765B1 (fr)

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Application Number Priority Date Filing Date Title
AT46287 1987-03-03
AT462/87 1987-03-03

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EP0280765A2 EP0280765A2 (fr) 1988-09-07
EP0280765A3 EP0280765A3 (en) 1989-03-08
EP0280765B1 true EP0280765B1 (fr) 1991-12-27

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EP (1) EP0280765B1 (fr)
AT (1) ATE70751T1 (fr)
DE (2) DE3775546D1 (fr)

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US5004495A (en) * 1990-02-05 1991-04-02 Labate M D Method for producing ultra clean steel
DE19505743A1 (de) * 1995-02-20 1996-08-22 Inteco Int Techn Beratung Verfahren und Anlage zum Herstellen von Blöcken aus Metallen
DE19807623A1 (de) * 1998-02-21 1999-08-26 Georg Fischer Disa Ag Niederdruck-Gießverfahren für Leichtmetalle, insbesondere Aluminium
DE102014110251A1 (de) * 2014-07-21 2016-01-21 Stephan Schwenkel Schmelzaggregat zum Einschmelzen von Gusswerkstoffen sowie ein Verfahren zur Herstellung einer Schmelze für das Gießen
CN116121549A (zh) * 2021-11-12 2023-05-16 东北大学 一种真空多功能电渣炉
CN115592096B (zh) * 2022-10-24 2023-06-20 华北理工大学 一种多炉加压浇铸生产碳氮协同超高氮钢装置及方法

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DE1236543B (de) * 1961-10-13 1967-03-16 Wilhelm Stich Dipl Ing Dr Tech Verfahren zur Hochdruck-Waermebehandlung im Vakuum hergestellten Stahles
BG35678A1 (en) * 1981-12-01 1984-06-15 Savov Method and device for treating and refining liquid alloys
LU84133A1 (de) * 1982-05-07 1984-03-07 Arbed Verfahren und vorrichtung zum metallurgischen behandeln von fluessigen metallen

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EP0280765A2 (fr) 1988-09-07
DE3775546D1 (de) 1992-02-06
ATE70751T1 (de) 1992-01-15
EP0280765A3 (en) 1989-03-08
DE3734406A1 (de) 1988-09-15

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