EP1470874A1 - Appareil pour la fabrication d'une masse métallique semi-solide thixotrope - Google Patents

Appareil pour la fabrication d'une masse métallique semi-solide thixotrope Download PDF

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Publication number
EP1470874A1
EP1470874A1 EP20030253449 EP03253449A EP1470874A1 EP 1470874 A1 EP1470874 A1 EP 1470874A1 EP 20030253449 EP20030253449 EP 20030253449 EP 03253449 A EP03253449 A EP 03253449A EP 1470874 A1 EP1470874 A1 EP 1470874A1
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EP
European Patent Office
Prior art keywords
sleeve
molten metals
semi
electromagnetic field
solid
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.)
Ceased
Application number
EP20030253449
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German (de)
English (en)
Inventor
Hong Chunpyo
Masayuki Itamura
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Individual
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Individual
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Publication date
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Publication of EP1470874A1 publication Critical patent/EP1470874A1/fr
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    • 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
    • B22D17/00Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007Semi-solid pressure die casting
    • 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
    • B22D27/02Use of electric or magnetic effects
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/12Making non-ferrous alloys by processing in a semi-solid state, e.g. holding the alloy in the solid-liquid phase

Definitions

  • the present invention relates to an apparatus for manufacturing a semi-solid metallic slurry, and more particularly, to an apparatus for manufacturing a semi-solid metallic slurry in a combined solid and liquid state, containing fine, uniform spherical particles.
  • Semi-solid metallic slurries refer to metallic materials, in a combined solid and liquid phase, which are intermediates manufactured by thixocasting, also expressed as rheocasting/thixocasting.
  • Semi-solid metallic slurries consist of spherical solid particles suspended in a liquid phase in an appropriate ratio at temperature ranges of a semi-solid state, and thus, they can be transformed even by a little force due to their thixotropic properties and can be easily cast like a liquid due to their high fluidity.
  • Rheocasting refers to a process of manufacturing billets or final products from metallic slurries with a predetermined viscosity through casting or forging.
  • Thixocasting refers to a process involving reheating billets, manufactured through rheocasting, back into semi-molten metallic slurries and casting or forging the metallic slurries to manufacture final products.
  • Such rheocasting/thixocasting is more advantageous than general forming processes using molten metals, such as casting or forging. Because semi-solid/semi-molten metallic slurries used in rheocasting/thixocasting have fluidity at a lower temperature than molten metals, it is possible to lower the die casting temperature, thereby ensuring an extended lifespan of the die. In addition, when semi-solid/semi-molten metallic slurries are extruded through a cylinder, turbulence is less likely to occur, and thus less air is incorporated during casting. Therefore, the formation of air pockets in final products is prevented.
  • semi-solid/semi-molten metallic slurries leads to reduced shrinkage during solidification, improved working efficiency, mechanical properties, and anti-corrosion, and lightweight products. Therefore, such semi-solid/semi-molten metallic slurries can be used as new materials in the fields of automobiles, airplanes, and electrical, electronic information communications equipment.
  • semi-solid metallic slurries are used both in rheocasting and thixocasting.
  • semi-solid slurries solidified from molten metals by a predetermined method are used in rheocasting
  • semi-molten slurries obtained by reheating solid billets are used in thixocasting.
  • the term, "semi-solid metallic slurries” means metallic slurries in a combined solid and liquid state at a temperature range, between the liquidus temperature and the solidus temperature of the metals, which can be manufactured by rheocasting through solidification of molten metals.
  • molten metals are stirred at a temperature of lower than the liquidus temperature while cooling, to break up dendritic structures into spherical particles suitable for rheocasting, for example, by mechanical stirring, electromagnetic stirring, gas bubbling, low-frequency, high-frequency, or electromagnetic wave vibration, electrical shock agitation, etc.
  • U.S. Patent No. 3,948,650 discloses a method and apparatus for manufacturing a liquid-solid mixture.
  • molten metals are vigorously stirred while cooled for solidification.
  • a semi-solid metallic slurry manufacturing apparatus disclosed in this patent uses a stirrer to induce flow of the solid-liquid mixture having a predetermined viscosity to break up dendritic crystalline structures or disperse broken dendritic crystalline structures in the liquid-solid mixture.
  • dendritic crystalline structures formed during cooling are broken up and used as nuclei for spherical particles.
  • the method causes problems of low cooling rate, manufacturing time increase, uneven temperature distribution in a mixing vessel, and non-uniform crystalline structure.
  • Mechanical stirring applied in the semi-solid metallic slurry manufacturing apparatus inherently leads to non-uniform temperature distribution in the mixing vessel.
  • the apparatus is operated in a chamber, it is difficult to continuously perform a subsequent process.
  • U.S. Patent No. 4,465,118 discloses a method and apparatus for manufacturing semi-solid alloy slurries.
  • This apparatus includes a coiled electromagnetic field application unit, a cooling manifold, and a die, which are sequentially formed inward, wherein molten metals are continuously loaded down into the vessel, and cooling water is flowed through the cooling manifold to cool the outer wall of the die.
  • molten metals are injected through a top opening of the die and cooled by the cooling manifold, thereby resulting in a solidification zone within the die.
  • a magnetic field is applied by the electromagnetic field application unit, cooling is allowed to break up dendritic crystalline structures formed in the solidification zone.
  • ingots are formed from the slurries and then pulled through the lower end of the apparatus.
  • the basic technical idea of this method and apparatus is to break up dendritic crystalline structures after solidification by applying vibration.
  • many problems arise with this method such as complicated processing and non-uniform particle structure.
  • the manufacturing apparatus since molten metals are continuously supplied to grow ingots, it is difficult to control the states of the metal ingots and the overall process.
  • the die prior to applying an electromagnetic field, the die is cooled using water, so that a great temperature difference exists between the peripheral and core regions of the die.
  • U. S. Patent No. 4,694,881 discloses a method for manufacturing thixotropic materials.
  • an alloy is heated to a temperature at which all metallic components of the alloy are present in a liquid phase, and the resulting molten metals are cooled to a temperature between their liquidus and solidus temperatures. Then, the molten metals are subjected to a shearing force in an amount sufficient to break up dendritic structures formed during the cooling of the molten metals to thereby manufacture the thixotropic materials.
  • Japanese Patent Application Laid-open Publication No. Hei. 11-33692 discloses a method for manufacturing metallic slurries for rheocasting.
  • molten metals are supplied into a vessel at a temperature near their liquidus temperature or of 50°C above their liquidus temperature.
  • the molten metals are subjected to a force, for example, ultrasonic vibration.
  • the molten metals are slowly cooled into the metallic slurries containing spherical particles.
  • This method also uses a physical force, such as ultrasonic vibration, to break up the dendrites grown at the early stage of solidification.
  • a physical force such as ultrasonic vibration
  • Japanese Patent Application Laid-open Publication No. Hei. 10-128516 discloses a casting method of thixotropic metals. This method involves loading molten metals into a vessel and vibrating the molten metals using a vibrating bar dipped in the molten metals to directly transfer its vibrating force to the molten metals. After forming a semi-solid and semi-liquid molten alloy, which contains nuclei, at a temperature range lower than its liquidus temperature, the molten alloy is cooled to a temperature at which it has a predetermined liquid fraction and then left stand from 30 seconds to 60 minutes to allow the nuclei to grow, thereby resulting in thixotropic metals.
  • this method provides relatively large particles of about 100 ⁇ m and takes a considerably long processing time, and cannot be performed in a vessel larger than a predetermined size.
  • U.S. Patent No. 6,432,160 discloses a method for making thixotropic metal slurries. This method involves simultaneously controlling the cooling and the stirring of molten metals to form the thixotropic metal slurries.
  • a stator assembly positioned around the mixing vessel is operated to generate a magnetomotive force sufficient to rapidly stir the molten metals in the vessel.
  • the molten metals are rapidly cooled by means of a thermal jacket, equipped around the mixing vessel, for precise temperature control of the mixing vessel and the molten metals.
  • the molten metals are continuously stirred in a manner such that when the solid fraction of the molten metals is low, a high stirring rate is provided, and when the solid fraction increases, a greater magnetomotive force is applied.
  • the present invention provides an apparatus for manufacturing a semi-solid metallic slurry containing fine, uniform spherical particles, with improvements in energy efficiency and mechanical properties, cost reduction, convenience of casting, and shorter manufacturing time.
  • the present invention also provides an apparatus for manufacturing a high-quality semi-solid metallic slurry within a short period of time, which can be readily and conveniently applied to a subsequent process.
  • the present invention also provides an apparatus for manufacturing and discharging a high-quality semi-solid metallic slurry in a convenient manner.
  • an apparatus for manufacturing a semi-solid metallic slurry comprising: at least one sleeve for receiving molten metals in liquid state; a stirring unit for applying an electromagnetic field to the molten metals in the sleeve; at least one plunger for defining the bottom of a space where the molten metals are loaded, the plunger being inserted into an end of the sleeve; and a driving unit for driving the plunger upward and downward.
  • the stirring unit may apply the electromagnetic field to the sleeve prior to loading the molten metals into the sleeve.
  • the stirring unit may apply the electromagnetic field to the sleeve simultaneously with or in the middle of loading the molten metals into the sleeve.
  • the stirring unit may apply the electromagnetic field to the sleeve until the loaded molten metals have a solid fraction of 0.001-0.7, preferably 0.001-0.4, and more preferably 0.001-0.1.
  • the molten metals in the sleeve may be cooled until they have a solid fraction of 0.1-0.7.
  • the apparatus may further comprise a temperature control element that is installed around the sleeve to cool the molten metals.
  • the temperature control element may comprise at least one of a cooler and a heater that are installed around the sleeve.
  • the temperature control element may cool the molten metals in the sleeve at a rate of 0.2-5.0°C/sec, preferably, 0.2-2.0°C/sec.
  • a method for manufacturing a semi-solid metallic slurry using the apparatus of the present invention involves stirring molten metals by applying an electromagnetic field prior to the completion of loading the molten metals into a sleeve.
  • electromagnetic stirring is performed prior to, simultaneously with, or in the middle of loading the molten metals into the sleeve, to prevent the formation of dendritic structures.
  • the stirring process may be performed using ultrasonic waves instead of the electromagnetic field.
  • molten metals are loaded into the sleeve.
  • the electromagnetic field is applied in an intensity sufficient to stir the molten metals.
  • molten metals are loaded into the sleeve at a temperature Tp.
  • an electromagnetic field may be applied to the sleeve prior to loading molten metals into the sleeve.
  • the present invention is not limited to this, and electromagnetic stirring may be performed simultaneously with or in the middle of loading the molten metals into the sleeve.
  • the molten metals Due to the electromagnetic stirring performed prior to the completion of loading molten metals into the sleeve, the molten metals do not grow into dendritic structures near the inner wall of the low temperature sleeve at the early stage of solidification. That is, numerous micronuclei are concurrently generated throughout the sleeve because all molten metals are rapidly cooled to a temperature lower than their liquidus temperature.
  • nuclei are created and uniformly dispersed throughout all molten metals in the sleeve.
  • the increased nuclei density reduces the distance between the nuclei, and spherical particles instead of dendritic particles are formed.
  • Tp loading temperature
  • an electromagnetic field is applied to a vessel when a portion of the molten metals reaches below their liquidus temperature. Accordingly, latent heat is generated due to the formation of solidification layers near the inner wall of the vessel at the early stage of cooling. Because the latent heat of solidification is about 400 times greater than the specific heat of the molten metals, significant time is required to drop the temperature of the entire molten metals below their liquidus temperature. Therefore, in such a conventional method, the molten metals are generally loaded into a vessel after the molten metals are cooled to a temperature near their liquidus temperature or a temperature of 50°C above their liquidus temperature.
  • the electromagnetic stirring may be stopped at any point after at least a portion of the molten metals in the sleeve reaches a temperature lower than the liquidus temperature T l , i.e., after accomplishing nucleation for a solid fraction of a predetermined amount such as about 0.001, as illustrated in FIG. 1. That is, an electromagnetic field may be applied to the molten metals in the sleeve throughout the cooling process of the molten metals and then stopped prior to a subsequent forming process such as die casting or hot forging. This is because, once nuclei are distributed uniformly throughout the sleeve, even at the time of growth of crystalline particles from the nuclei, properties of the metallic slurry are not affected by the electromagnetic stirring.
  • the electromagnetic stirring can be carried out until a solid fraction of the molten metals is 0.001-0.7.
  • it is preferable to carry out the electromagnetic stirring until a solid fraction of the molten metals is in a range of 0.001-0.4, and more preferably, 0.001-0.1.
  • the metallic slurry is discharged from the sleeve for a continuous subsequent process, for example, die casting, hot forging, and billet formation.
  • the sleeve After an electromagnetic field is applied and prior to completion of loading the molten metals into the sleeve to form uniformly distributed nuclei, the sleeve is cooled to facilitate the growth of the nuclei. This cooiing process may be performed simultaneously with loading the molten metals into the sleeve.
  • an electromagnetic field may be continuously applied during the cooling process.
  • cooling may be performed even when the electromagnetic field is applied to the sleeve.
  • the manufactured semi-solid metallic slurry can be immediately used in a subsequent forming process.
  • the cooling process may be carried out just prior to a subsequent forming process, and preferably, until a solid fraction of the molten metals is 0.1-0.7, i.e., up to time t 2 of FIG. 1.
  • the molten metals may be cooled at a rate of 0.2-5.0°C/sec.
  • the cooling rate may be 0.2-2.0°C/sec depending on a desired distribution of nuclei and a desired size of particles.
  • a semi-solid metallic slurry containing a predetermined amount of solid fraction can be easily manufactured.
  • the manufactured semi-solid metallic slurry is directly subjected to billet formation process for forming a billet for thixocasting using rapid cooling, or, alternatively, die casting, forging, or pressing process for forming final products.
  • a semi-solid metallic slurry can be manufactured within a short period of time. That is, manufacturing of a metallic slurry with a solid fraction of 0.1-0.7 occurs within merely 30-60 seconds from loading the molten metals into the sleeve.
  • the manufactured metallic slurry can be used for forming products having uniform, dense spherical crystalline structures.
  • the aforementioned method for manufacturing a semi-solid metallic slurry can be performed using an apparatus according to an embodiment of the present invention as shown in FIGS. 2 and 3.
  • a semi-solid metallic slurry manufacturing apparatus comprises at least one sleeve 2 for receiving molten metals in liquid state; a stirring unit 1 for applying an electromagnetic field to the molten metals; at least one plunger 5 for defining the bottom of a space where the molten metals are loaded, the plunger being inserted into an end of the sleeve; and a driving unit 3 for driving the plunger 5 upward and downward.
  • the stirring unit 1 is mounted on the top of a hollow base plate 14.
  • the base plate 14 is supported by a support member 15, installed at a predetermined height from the ground.
  • the coil 11 for applying an electromagnetic field is mounted on the base plate 14, while being supported by a frame 12 having an inner space 13.
  • the coil 11 is electrically connected to a controller (not shown) and applies a predetermined intensity of electromagnetic field toward the space 13 to electromagnetically stir the molten metals contained in the sleeve 2 placed in the space 13.
  • the stirring unit 1 may be an ultrasonic stirrer.
  • the sleeve 2 may be placed inside the stirring unit 1, i.e., in the space 13.
  • the sleeve 2 may be fixed on the base plate 14 while in contact with the frame 12.
  • the sleeve 2 may be made of a metallic material or an insulating material. However, it is preferable to use the sleeve 2 made of a material having a higher melting point than the molten metals to be loaded thereinto.
  • the lower end of the sleeve 2 is closed by the plunger 5 and the upper end of the sleeve 2 is open for receiving molten metals. That is, the sleeve 2 may be in the form of a vessel with a bottom defined by the plunger 5.
  • thermocouple may be installed in the sleeve 2 while the thermocouple is connected to the controller for providing temperature information to the controller.
  • the apparatus of the present invention may further comprise a temperature control element 20 that is installed around the sleeve 2, as shown in FIG. 3.
  • the temperature control element 20 is comprised of a cooler and/or a heater.
  • a water jacket 22 acts as the cooler and an electric heating coil 23 acts as the heater.
  • the water jacket 22 is installed around the sleeve 2 and contains a cooling water pipe 21.
  • the electric heating coil 23 is installed around the water jacket 22.
  • the cooling water pipe 21 may be buried in the sleeve 2 and other heating means except for the electric heating coil 23 may be used.
  • Molten metals contained in the sleeve 2 can be cooled at an appropriate rate using the temperature control element 20. It is understood that such a sleeve 2 can be applied to all of the following embodiments of a semi-solid metallic slurry manufacturing apparatus according to the present invention. Molten metals contained in the sleeve 2 may be cooled using the temperature control element 20 or spontaneously.
  • the lower end of the plunger 5 is connected to a piston rod 51, which is in turn coupled with the driving unit 3.
  • the driving unit 3 comprises a driving motor and a gear or a hydraulic cylinder, etc.
  • the driving unit 3 further comprises a power system 31 electrically connected to the controller.
  • a loading unit 4 may be used as means for providing molten metals to the sleeve 2.
  • a general ladle which is electrically connected to the controller, may be used.
  • a furnace for forming molten metals may be directly connected to the loading unit 4. Any devices for loading molten metal into the sleeve 2 can be used as the loading unit 4.
  • the sleeve 2 is cooled at a predetermined rate until a solid fraction of a resultant semi-solid metallic slurry S is in a range of 0.1-0.7.
  • the cooling may be carried out at a rate of 0.2-5.0°C/sec, preferably 0.2-2.0°C/sec.
  • the cooling may be carried out by the temperature control element 20 but is not limited thereto. It is understood that the molten metals contained in the sleeve 2 may be spontaneously cooled without the aid of the temperature control element 20.
  • the application of an electromagnetic field may be sustained until the cooling is completed, i.e., a solid fraction of the resultant semi-solid metallic slurry is in the range of at least 0.001-0.7.
  • a solid fraction of the resultant semi-solid metallic slurry is in the range of at least 0.001-0.7.
  • the time required for these solid fraction levels can be determined by previous experiments. It is understood that the cooling can be performed during the application of the electromagnetic field, as described above.
  • the driving unit 3 is operated to raise the plunger 5, as shown in FIG. 5. Therefore, the slurry S is drawn out from the sleeve 2 and then transferred to an apparatus for a subsequent forming process, such as rheocasting process, by a transfer unit such as a robot.
  • the semi-solid metallic slurry manufacturing apparatus of the present invention can continuously manufacture semi-solid metallic slurries in a large scale and can be readily and conveniently applied to a subsequent process. Therefore, the total process efficiency is improved.
  • the apparatus for manufacturing a semi-solid metallic slurry according to the present invention can be used for rheocasting of various kinds of metals and alloys, for example, aluminum, magnesium, zinc, copper, iron, and alloys thereof.
  • Semi-solid metallic slurries manufactured according to the present invention contain spherical microparticles of uniform distribution with an average size of 10-60 ⁇ m.
  • Such uniform spherical particles can be formed within a short time through electromagnetic stirring at a temperature above the liquidus temperature of molten metals to thereby generate more nuclei near inner vessel walls.
  • the overall slurry manufacturing process can be simplified, and the duration of electromagnetic stirring and forming time can be greatly shortened, thereby saving energy for the stirring and costs.
  • the semi-solid metallic slurry manufacturing apparatus makes it convenient to perform a subsequent process and increases the yield of formed products.
  • the apparatus structure is relatively simple and thus a large amount of semi-solid slurries can be rapidly manufactured in a convenient manner.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
EP20030253449 2003-04-24 2003-06-02 Appareil pour la fabrication d'une masse métallique semi-solide thixotrope Ceased EP1470874A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020030025998A KR100436118B1 (ko) 2003-04-24 2003-04-24 반응고 금속 슬러리 제조장치
KR2003025998 2003-04-24

Publications (1)

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EP1470874A1 true EP1470874A1 (fr) 2004-10-27

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EP20030253449 Ceased EP1470874A1 (fr) 2003-04-24 2003-06-02 Appareil pour la fabrication d'une masse métallique semi-solide thixotrope

Country Status (5)

Country Link
US (1) US20040211540A1 (fr)
EP (1) EP1470874A1 (fr)
JP (1) JP3520994B1 (fr)
KR (1) KR100436118B1 (fr)
CN (1) CN1248806C (fr)

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US7816250B2 (en) * 2006-09-29 2010-10-19 Intel Corporation Composite solder TIM for electronic package
KR101251275B1 (ko) * 2007-07-13 2013-04-10 현대자동차주식회사 반응고 슬러리 제조용 전자 교반 장치
CN103056318B (zh) 2008-03-05 2017-06-09 南线有限责任公司 作为熔融金属中的防护屏蔽层的铌
DK2556176T3 (da) 2010-04-09 2020-05-04 Southwire Co Llc Ultralydsafgasning af smeltede metaller
US8652397B2 (en) 2010-04-09 2014-02-18 Southwire Company Ultrasonic device with integrated gas delivery system
KR101256616B1 (ko) 2010-06-22 2013-04-19 신닛테츠스미킨 카부시키카이샤 연속주조장치
PL3071718T3 (pl) 2013-11-18 2020-02-28 Southwire Company, Llc Sondy ultradźwiękowe z wylotami gazu dla odgazowywania stopionych metali
ES2784936T3 (es) 2015-02-09 2020-10-02 Hans Tech Llc Refinado de grano por ultrasonidos
US10233515B1 (en) 2015-08-14 2019-03-19 Southwire Company, Llc Metal treatment station for use with ultrasonic degassing system
CN108348993B (zh) 2015-09-10 2022-02-01 南线有限责任公司 熔融金属处理装置、形成金属产品的方法、系统和铸造机
CN105127393B (zh) * 2015-09-21 2017-05-31 珠海市润星泰电器有限公司 一种连续制备半固态浆料的工艺及设备
CN107824752B (zh) * 2017-11-29 2023-10-03 南昌大学 一种制备金属半固态浆料的装置
KR102121979B1 (ko) 2018-10-24 2020-06-12 주식회사 퓨쳐캐스트 가동형 전자기제어 조직제어모듈을 구비하는 다이캐스팅 장치
CN109732054A (zh) * 2019-02-02 2019-05-10 东营源纳合金科技有限公司 一种特种铝合金半固态材料制备及自动化成型装置
KR102249385B1 (ko) * 2019-05-31 2021-05-10 한주금속(주) 반응고 고압 주조설비의 전자기 진동 교반장치
CN113634724B (zh) * 2020-05-10 2022-11-18 昆山祁御新材料科技有限公司 超细高纯金属坯料制备方法与装置

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US4450893A (en) * 1981-04-27 1984-05-29 International Telephone And Telegraph Corporation Method and apparatus for casting metals and alloys
US4465118A (en) * 1981-07-02 1984-08-14 International Telephone And Telegraph Corporation Process and apparatus having improved efficiency for producing a semi-solid slurry
EP0490463A1 (fr) * 1990-12-10 1992-06-17 Inland Steel Company Procédé et dispositif pour coulée de gelées métalliques

Also Published As

Publication number Publication date
KR100436118B1 (ko) 2004-06-16
CN1539573A (zh) 2004-10-27
US20040211540A1 (en) 2004-10-28
JP2004322203A (ja) 2004-11-18
CN1248806C (zh) 2006-04-05
JP3520994B1 (ja) 2004-04-19

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