EP2393619B1 - Procédé de fabrication de pièces moulées sous pression - Google Patents

Procédé de fabrication de pièces moulées sous pression Download PDF

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Publication number
EP2393619B1
EP2393619B1 EP10743166A EP10743166A EP2393619B1 EP 2393619 B1 EP2393619 B1 EP 2393619B1 EP 10743166 A EP10743166 A EP 10743166A EP 10743166 A EP10743166 A EP 10743166A EP 2393619 B1 EP2393619 B1 EP 2393619B1
Authority
EP
European Patent Office
Prior art keywords
aluminum alloy
working space
nanoparticles
oxide
kneading
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
Application number
EP10743166A
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German (de)
English (en)
Other versions
EP2393619A1 (fr
Inventor
Rüdiger Franke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rheinfelden Alloys GmbH and Co KG
Original Assignee
Rheinfelden Alloys GmbH and Co KG
Priority date (The priority date 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 date listed.)
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Publication date
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Application filed by Rheinfelden Alloys GmbH and Co KG filed Critical Rheinfelden Alloys GmbH and Co KG
Priority to EP10743166A priority Critical patent/EP2393619B1/fr
Priority to PL10743166T priority patent/PL2393619T3/pl
Priority to SI201030249T priority patent/SI2393619T1/sl
Publication of EP2393619A1 publication Critical patent/EP2393619A1/fr
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Classifications

    • 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
    • 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
    • B22D17/00Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/08Cold chamber machines, i.e. with unheated press chamber into which molten metal is ladled
    • B22D17/10Cold chamber machines, i.e. with unheated press chamber into which molten metal is ladled with horizontal press motion
    • 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
    • B22D17/20Accessories: Details
    • B22D17/30Accessories for supplying molten metal, e.g. in rations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00Special casting characterised by the nature of the product
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C26/00Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C26/00Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002Carbon nanotubes

Definitions

  • the invention relates to a method for the production of die cast parts from an aluminum alloy according to the preamble of claim 1.
  • molten metal in a liquid state is filled in a cylinder tube in which a push rod is coaxially arranged.
  • the outer diameter of the push rod here is smaller than the inner diameter of the cylinder tube, so that the liquid metal flows in the space between the cylinder tube and push rod.
  • the push rod is provided to effect axial reciprocation and rotation about its longitudinal axis.
  • a valve surrounding the push rod and slidable on the inner wall of the cylinder tube while overcoming a frictional resistance divides the cylinder tube into upper and lower chambers. Depending on the axial displacement direction of the push rod, the valve opens and closes, allowing or blocking the flow of metal between the upper and lower chambers.
  • the valve As the push rod advances, the valve remains closed and the metal in the lower chamber of the cylinder tube is pushed through an outlet opening into the fill chamber of a die casting machine.
  • the temperature profile of the molten metal in the cylinder tube is controlled so that adjusts a partially solid melt with a certain solids content.
  • From the lateral surface of the push rod wings protrude radially.
  • the wings serve on the one hand, the coaxial storage of the push rod in the cylinder tube by the wings are supported on the inner wall of the cylinder tube.
  • the blades lead by the rotation of the push rod about its longitudinal axis to a stirring of the molten metal with the aim of a uniform temperature distribution in the metal.
  • the invention has for its object to provide a method of the type mentioned, with which continuously a partially solid aluminum alloy melt can be provided inexpensively and further processed to die-cast parts.
  • Another object of the invention is to provide a process for the production of nanoparticle-reinforced aluminum alloy die-cast parts, with which a partially solid aluminum alloy melt continuously under the action of process-typical
  • Shear forces with a high fine dispersion of nanoparticles can be inexpensively provided and further processed into die-cast parts.
  • the solution of the second object according to the invention results in nanoparticles in the mixing and kneading machine being mixed with the aluminum alloy and finely dispersed by high shear forces in the aluminum alloy to produce nanoparticle-reinforced die-cast parts, with liquid aluminum alloy and nanoparticles at one end of the housing facing the working space supplied and removed at the other end of the housing the working space as a partially solid aluminum alloy with a predetermined solid content and with finely dispersed in the aluminum alloy nanoparticles.
  • the high shear forces present in the partially solidified phase state in the kneading process cause, in addition to the comminution of forming dendritic branches and the higher ductility thus achieved, a fine dispersion of the nanoparticles which is required for their strength-increasing effect.
  • the inner housing shell is surrounded by an outer housing shell to form a preferably hollow cylindrical space and for cooling and heating of the working space cold and / or hot gases are passed through the gap.
  • cold and / or hot gases are passed through the gap.
  • hot gases preferably combustion gases
  • the gases are preferably passed in countercurrent to the transport direction of the aluminum alloy through the gap.
  • the solid content of the aluminum alloy is preferably adjusted to 40 to 80%, in particular to more than 50%.
  • the partially solid aluminum alloy is removed from the working space as a semi-solid metal strand.
  • the continuously emerging, partially solid metal strand is subdivided into partially solid metal portions and the partially solid metal portions are transferred into the filling chamber of the die casting machine.
  • the weight fraction of the nanoparticles in the alloy is preferably between about 0.1 to 10%.
  • Suitable, inexpensive nanoparticles are preferably made of fumed silica, such as. B. Aerosil ®.
  • other nanoparticles can be used, such as.
  • As the known carbon nanotubes (carbon nanotubes, CNT), and other, for example, according to the known Aerosil ® method produced nanoscale particles of metal and Halbmetalloxiden, such as. Example, alumina (Al 2 O 3 ), titanium dioxide (TiO 2 ), zirconium oxide (ZrO 2 ), antimony (III) oxide, chromium (III) oxide, iron (III) oxide germanium (IV) oxide, vanadium (V) oxide or tungsten (VI) oxide.
  • the system for die casting of aluminum alloy die castings optionally reinforced with nanoparticles has a die casting machine 10 and one of the die casting machine 10 prefixed mixing and kneading machine 30.
  • the only partially reproduced in the drawing die casting machine 10 is a commercially available machine for conventional die casting of aluminum alloys and has u. a. a filling chamber 12 connected to a fixed side 18 of a casting mold and having an opening 16 for receiving the metal to be ejected from the filling chamber 12 by means of a piston 20 and to be injected into a mold cavity 14 of the casting mold.
  • the mixing and kneading machine 30 is in the FIGS. 2 and 3 shown in detail.
  • the basic structure of such a mixing and kneading machine is for example from the CH-A-278 575 known.
  • the mixing and kneading machine 30 has a housing 31 with a working space 34 enclosed by an inner housing jacket 32, in which a worm shaft 36 which rotates in the inner housing jacket 32 about a longitudinal axis x and translates in the longitudinal axis x is arranged.
  • the worm shaft 36 is interrupted in the circumferential direction to form individual Kneteriel 38. In this way arise between the individual kneading blades 38 axial passage openings 40.
  • the working chamber 34 delimiting, cylindrical inner housing shell 32 of the mixing and kneading machine 30 is of a cylindrical outer housing shell 46 surrounded.
  • the inner housing shell 32 and the outer housing shell 46 form a double jacket and enclose a hollow cylindrical space 48.
  • a filling opening 50 for supplying liquid aluminum alloy and optionally nanoparticles into the working space 34 is provided. Although only one fill opening 50 is shown in the drawing, two separate fill openings may be provided for the aluminum alloy and for the nanoparticles. In principle, it is also possible to mix the nanoparticles of the liquid aluminum alloy into the kneading and mixing machine 30 before the metal is introduced.
  • an outlet opening 52 is provided for removing semi-solid aluminum alloy with optionally dispersed nanoparticles in it.
  • inlet openings 54, 56 for introducing cold or hot gases into the intermediate space 48 are provided in the outer housing shell 46.
  • outlet openings 58, 60 for the exit of the gases from the intermediate space 48 are provided on the end of the housing 36 near the drive end of the worm shaft.
  • Fig. 4 shows a schematic representation of characteristic shear and Dehnungsströmfelder in a product mass P, as in a trained in the prior art mixing and kneading machine 30 through a a kneading stud 42 passing Knethoff 38 occur.
  • the direction of rotation of the kneading blade 38 is schematically indicated by a curved arrow A, while the translational movement of the kneading blade 38 is indicated by a double arrow B. Due to the rotational movement of the kneading blade 38 whose tip divides the product mass P, as indicated by arrows C, D.
  • a maximum approximation of kneading blade 38 and kneading pin 42 is produced per shear cycle by the sinusoidal axial movement of the respective kneading blade 38 on a line and thus a maximum shear rate in the product mass P.
  • An aluminum alloy melt held just above the liquidus temperature of the alloy is metered into the working space 34 alone or together with nanoparticles via the filling opening 50.
  • By crushing the partially solidified aluminum alloy with nanoparticles between the kneading blades 38 and the kneading pin 42 high shear forces are applied, which lead both to the comminution of dendrite branches and cause fine dispersion of the present in the form of agglomerates nanoparticles.
  • An efficient, homogenizing mixing results from the superposition of radial and longitudinal mixing effect.
  • the solid portion of the aluminum alloy in the working space 34 is so is set to be in the desired range upon removal of the metal through the outlet port 52.
  • the desired solid content of the aluminum alloy is adjusted by measuring the change in the viscosity of the molten metal in the kneading and mixing machine 30.
  • the viscosity increasing with increasing solid fraction of the partially solid aluminum alloy can be detected, for example, by measuring the rotational resistance on the drive shaft 44 of the worm shaft 36.
  • By determining the rotational resistance for defined fixed fractions it is possible to determine corresponding setpoint values to which measured actual values are regulated by controlling the flow of cold and hot gases through the intermediate space 48 between the inner and outer housing shells 32, 46.
  • the aluminum alloy containing the desired solid fraction and optionally finely dispersed nanoparticles is introduced via the filling opening 16 into the filling chamber 12 of the die casting machine 10 and cyclically shot from the filling chamber 12 into the mold cavity 14 of the casting mold by the piston 20 in a known manner.
  • the aluminum alloy containing the desired solid fraction and optionally finely dispersed nanoparticles is continuously ejected via the outlet opening 52 in the form of a partially solid metal strand 70.
  • partially solid metal portions 72 are cut to length, for example, with a rotating knife.
  • the partially fixed metal portions 72 usually correspond to those for the production of a single die casting required amount of metal and are transferred individually for each shot in the filling chamber 12 of the die casting machine 10 and shot from this intermittently by means of the piston 20 in a known manner from the filling chamber 12 into the mold cavity 14 of the mold.
  • the semi-solid metal strand 70 leaves the mixing and kneading machine 30 in the direction of the longitudinal axis x of the worm shaft 36 in the horizontal direction, but is also another, z. B. vertical, exit direction conceivable.
  • the cross section of the metal strand 70 depends on the cross section of the outlet opening 52 and is usually circular.
  • the partially fixed metal portions 72 can be gripped, for example, with a pair of pliers and transferred into the filling chamber 12 of the die casting machine 10.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Continuous Casting (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (10)

  1. Procédé de fabrication de pièces moulées sous pression en un alliage d'aluminium, dans lequel l'alliage d'aluminium traverse une machine comportant une enceinte (31) avec une chambre de travail (34) entourée par une enveloppe d'enceinte intérieure (32) et avec un arbre muni d'ailettes tournant autour d'un axe longitudinal (x) dans l'enveloppe d'enceinte intérieure (32) et se déplaçant en translation alternée selon l'axe longitudinal (x), dans lequel on introduit l'alliage d'aluminium liquide dans la chambre de travail (34) à une extrémité de l'enceinte (31) et on le prélève hors de la chambre de travail (34) à l'autre extrémité de l'enceinte (31) sous la forme d'un alliage d'aluminium partiellement solide avec une proportion de solide prédéterminée, on le transfère dans une chambre de remplissage (12) d'une machine de coulée sous pression (10) et on le refoule dans un moule de coulée au moyen d'un piston (20), dans lequel on règle la proportion de solide de l'alliage d'aluminium à la proportion de solide prédéterminée dans la chambre de travail (34) par un refroidissement et un chauffage ciblés de la chambre de travail (34), caractérisé en ce que l'on soumet l'alliage d'aluminium à des forces de cisaillement élevées dans une machine de mélange et de pétrissage (30) avec un arbre à vis sans fin (36) interrompu en direction périphérique en formant des ailettes de pétrissage individuelles (38) avec des ouvertures de passage (40) entre les ailettes de pétrissage (38) et avec des plots de pétrissage (42) fixés à l'enveloppe d'enceinte intérieure (32), pénétrant dans la chambre de travail (34) et s'engageant dans les ouvertures de passage axiales (40).
  2. Procédé selon la revendication 1, caractérisé en ce que l'enveloppe d'enceinte intérieure (32) est entourée par une enveloppe d'enceinte extérieure (46) en formant une chambre intermédiaire (48) de préférence cylindrique creuse et on conduit des gaz froids et/ou chauds à travers la chambre intermédiaire (48) pour refroidir et chauffer la chambre de travail (34).
  3. Procédé selon la revendication 2, caractérisé en ce que l'on conduit pour le refroidissement de l'air, de préférence de l'air comprimé, et pour le chauffage des gaz chauds, de préférence des gaz de combustion, à travers la chambre intermédiaire (48).
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que l'on conduit les gaz à travers la chambre intermédiaire (48) à contre-courant par rapport à la direction de transport de l'alliage d'aluminium.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que, pour le réglage d'une proportion de solide désirée, on mesure la viscosité de l'alliage d'aluminium dans la chambre de travail (34) et on la règle à une valeur prédéterminée par un refroidissement et un chauffage ciblés de la chambre de travail (34).
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on règle la proportion de solide de l'alliage d'aluminium à 40 à 80 %, de préférence à plus de 50 %.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on prélève l'alliage d'aluminium partiellement solide hors de la chambre de travail (34) sous la forme d'une barre métallique partiellement solide (70), on divise la barre métallique partiellement solide (70) en portions métalliques partiellement solides (72) et on transfère les portions métalliques partiellement solides (72) dans la chambre de remplissage (12) de la machine de coulée sous pression (10).
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que, pour la fabrication de pièces moulées sous pression renforcées par des nanoparticules, on mélange des nanoparticules avec l'alliage d'aluminium dans la machine de mélange et de pétrissage (30) et on les disperse finement dans l'alliage d'aluminium à l'aide de forces de cisaillement élevées, dans lequel on introduit l'alliage d'aluminium liquide et des nanoparticules dans la chambre de travail (34) à une extrémité de l'enceinte (31) et on les prélève hors de la chambre de travail (34) à l'autre extrémité de l'enceinte (31) sous la forme d'un alliage d'aluminium partiellement solide avec une proportion de solide prédéterminée et avec des nanoparticules finement dispersées dans l'alliage d'aluminium.
  9. Procédé selon la revendication 8, caractérisé en ce que la part en volume des nanoparticules dans l'alliage vaut 0,1 à 10 %.
  10. Procédé selon la revendication 9, caractérisé en ce que l'on utilise comme nanoparticules l'acide silicique pyrogène, des nanotubes de carbone (carbon nanotubes, CNT), ainsi que d'autres particules nanométriques d'oxydes de métaux et de métalloïdes, comme par exemple l'oxyde d'aluminium (Al2O3), le dioxyde de titane (TiO2), l'oxyde de zirconium (ZrO2), l'oxyde d'antimoine(III), l'oxyde de chrome(III), l'oxyde de fer(III), l'oxyde de germanium(IV), l'oxyde de vanadium(V) ou l'oxyde de tungstène(VI).
EP10743166A 2010-03-24 2010-08-19 Procédé de fabrication de pièces moulées sous pression Not-in-force EP2393619B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10743166A EP2393619B1 (fr) 2010-03-24 2010-08-19 Procédé de fabrication de pièces moulées sous pression
PL10743166T PL2393619T3 (pl) 2010-03-24 2010-08-19 Metoda wytwarzania elementów odlewanych ciśnieniowo
SI201030249T SI2393619T1 (sl) 2010-03-24 2010-08-19 Postopek izdelave pod pritiskom vlitih delov

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10157519 2010-03-24
EP10743166A EP2393619B1 (fr) 2010-03-24 2010-08-19 Procédé de fabrication de pièces moulées sous pression
PCT/EP2010/062089 WO2011116838A1 (fr) 2010-03-24 2010-08-19 Procédé de fabrication de pièces moulées sous pression

Publications (2)

Publication Number Publication Date
EP2393619A1 EP2393619A1 (fr) 2011-12-14
EP2393619B1 true EP2393619B1 (fr) 2013-04-03

Family

ID=42167439

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10743166A Not-in-force EP2393619B1 (fr) 2010-03-24 2010-08-19 Procédé de fabrication de pièces moulées sous pression

Country Status (16)

Country Link
US (1) US20130220568A1 (fr)
EP (1) EP2393619B1 (fr)
KR (1) KR20130055563A (fr)
CN (1) CN102834203A (fr)
AU (1) AU2010349399A1 (fr)
BR (1) BR112012023916A2 (fr)
CA (1) CA2792432A1 (fr)
DK (1) DK2393619T3 (fr)
ES (1) ES2423326T3 (fr)
HR (1) HRP20130605T1 (fr)
MX (1) MX2012010807A (fr)
PL (1) PL2393619T3 (fr)
PT (1) PT2393619E (fr)
RU (1) RU2012143377A (fr)
SI (1) SI2393619T1 (fr)
WO (1) WO2011116838A1 (fr)

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EP2522885A1 (fr) 2011-05-11 2012-11-14 Rheinfelden Alloys GmbH & Co. KG Agencement d'étanchéification
EP2564953A1 (fr) * 2011-09-05 2013-03-06 Rheinfelden Alloys GmbH & Co. KG Procédé de production de pièces formées
CN103008610B (zh) * 2012-12-18 2015-05-27 华南理工大学 锌合金蜗轮的挤压铸造方法
AT518824A1 (de) * 2016-05-31 2018-01-15 Lkr Leichtmetallkompetenzzentrum Ranshofen Gmbh Verfahren zur Herstellung eines Profils aus einer Metalllegierung
AT518825A1 (de) * 2016-05-31 2018-01-15 Lkr Leichtmetallkompetenzzentrum Ranshofen Gmbh Verfahren zur Herstellung eines Profils aus einer Metalllegierung
DE102021203642B3 (de) 2021-04-13 2022-09-08 Volkswagen Aktiengesellschaft Lagerkern für ein Gummi-Metalllager, Gummi-Metalllager und Kraftfahrzeug mit einem solchen

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PT1815958E (pt) * 2006-02-06 2008-10-28 Buss Ag Máquina de misturar e amassar
US7837811B2 (en) * 2006-05-12 2010-11-23 Nissei Plastic Industrial Co., Ltd. Method for manufacturing a composite of carbon nanomaterial and metallic material
JP4224083B2 (ja) * 2006-06-15 2009-02-12 日精樹脂工業株式会社 複合金属材料の製造方法及び複合金属成形品の製造方法

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RU2012143377A (ru) 2014-05-10
US20130220568A1 (en) 2013-08-29
BR112012023916A2 (pt) 2016-08-02
EP2393619A1 (fr) 2011-12-14
KR20130055563A (ko) 2013-05-28
CA2792432A1 (fr) 2011-09-29
HRP20130605T1 (en) 2013-08-31
AU2010349399A1 (en) 2012-09-27
PT2393619E (pt) 2013-07-09
ES2423326T3 (es) 2013-09-19
WO2011116838A1 (fr) 2011-09-29
MX2012010807A (es) 2013-01-22
CN102834203A (zh) 2012-12-19
DK2393619T3 (da) 2013-07-08
SI2393619T1 (sl) 2013-08-30

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